JP7371729B2 - Chemical mechanical polishing composition and chemical mechanical polishing method - Google Patents
Chemical mechanical polishing composition and chemical mechanical polishing method Download PDFInfo
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- JP7371729B2 JP7371729B2 JP2022096331A JP2022096331A JP7371729B2 JP 7371729 B2 JP7371729 B2 JP 7371729B2 JP 2022096331 A JP2022096331 A JP 2022096331A JP 2022096331 A JP2022096331 A JP 2022096331A JP 7371729 B2 JP7371729 B2 JP 7371729B2
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- Prior art keywords
- chemical mechanical
- mechanical polishing
- polishing
- alumina
- acid
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- 239000011347 resin Substances 0.000 claims description 95
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Images
Description
本発明は、化学機械研磨用組成物及び化学機械研磨方法に関する。 The present invention relates to a chemical mechanical polishing composition and a chemical mechanical polishing method.
多層回路基板（多層化された回路基板）では、配線パターンが形成された複数の回路基板が積層した三次元的な配線構造が要求されている。多層回路基板に凹凸や湾曲が生じないように、多層回路基板を構成する各層の回路基板は均一な厚みを有しかつ表面が平坦であるように形成される必要がある。 A multilayer circuit board (multilayer circuit board) is required to have a three-dimensional wiring structure in which a plurality of circuit boards on which wiring patterns are formed are stacked. In order to prevent unevenness or curvature in the multilayer circuit board, each layer of the circuit board constituting the multilayer circuit board needs to be formed to have a uniform thickness and a flat surface.
配線パターンを有する回路基板の製造方法としては、例えば、基板の表面に所望の配線パターンに対応した凹部を形成し、この表面全体にメッキにより導電層を形成した後、基板の表面側を研磨して凹部のみに導電層が残るようにする方法がある。基板を研磨する方法としては、例えば、バフ研磨等の細かい砥粒を用いた研磨方法（例えば、特許文献１参照）、スラリーを用いた化学機械研磨方法（例えば、特許文献２～３参照）等が検討されている。この特許文献３では、大型な配線構造体を形成する際の回路基板を研磨する方法として、スラリー中の有機酸及び水溶性高分子の含有割合を調整する方法が検討されている。 As a method for manufacturing a circuit board having a wiring pattern, for example, a recess corresponding to a desired wiring pattern is formed on the surface of the board, a conductive layer is formed on the entire surface by plating, and then the front side of the board is polished. There is a method in which the conductive layer remains only in the recesses. Examples of methods for polishing the substrate include polishing methods using fine abrasive grains such as buffing (see, for example, Patent Document 1), chemical mechanical polishing methods using slurry (see, for example, Patent Documents 2 and 3), etc. is being considered. In Patent Document 3, as a method of polishing a circuit board when forming a large wiring structure, a method of adjusting the content ratio of an organic acid and a water-soluble polymer in a slurry is studied.
特許文献３のような従来の回路基板形成における化学機械研磨方法では、銅などの配線金属を高速で研磨する方法が検討されている。しかしながら、回路基板には、配線金属だけでなく樹脂膜も多く含まれており、特に配線上に樹脂膜が多く存在するような回路基板において、膜厚の厚い樹脂膜を化学機械研磨により高速研磨でき、かつ、高平坦化できる技術に対するニーズが存在する。また、不要な樹脂膜を研磨除去した後に表出する配線金属／樹脂膜が共存する被研磨面においても、化学機械研磨により高平坦化でき、かつ、スクラッチの発生を低減できる技術に対するニーズも存在する。 In a conventional chemical mechanical polishing method for forming a circuit board as disclosed in Patent Document 3, a method of polishing wiring metal such as copper at high speed is being considered. However, circuit boards contain not only metal wiring but also a large amount of resin film, and especially in circuit boards where there is a large amount of resin film on the wiring, it is difficult to polish the thick resin film at high speed using chemical mechanical polishing. There is a need for a technology that can achieve high flatness. In addition, there is a need for a technology that can achieve high flatness by chemical mechanical polishing and reduce the occurrence of scratches even on the polished surface where wiring metal/resin films coexist, which are exposed after removing unnecessary resin films. do.
そこで、本発明に係る幾つかの態様は、配線金属及び樹脂膜を有する回路基板を化学機械研磨する際に、樹脂膜に対する研磨速度が十分に高く、かつ、被研磨面の高平坦化及びスクラッチ発生の低減を実現できる化学機械研磨方法、及び配線金属や樹脂膜に対する研磨速度が十分に高く、かつ、被研磨面を高平坦化できる化学機械研磨用組成物を提供するものである。 Accordingly, some aspects of the present invention are aimed at achieving a sufficiently high polishing rate for the resin film, high flattening of the surface to be polished, and scratch-free polishing when chemically mechanically polishing a circuit board having a wiring metal and a resin film. The object of the present invention is to provide a chemical mechanical polishing method that can reduce the occurrence of polishing, and a chemical mechanical polishing composition that has a sufficiently high polishing rate for wiring metals and resin films and can highly flatten the surface to be polished.
本発明は上述の課題の少なくとも一部を解決するためになされたものであり、以下のいずれかの態様として実現することができる。 The present invention has been made to solve at least part of the above-mentioned problems, and can be realized in any of the following embodiments.
本発明に係る化学機械研磨用組成物の一態様は、
（Ａ１）アルミナ含有粒子と、
（Ｂ）有機酸と、
を含有し、
前記（Ａ１）アルミナ含有粒子は、粉末Ｘ線回折パターンにおける回折強度が最大となるピーク部分の半値幅が０．３０°未満のものである。
One embodiment of the chemical mechanical polishing composition according to the present invention is
(A1) alumina-containing particles;
(B) an organic acid;
Contains
The alumina-containing particles (A1) have a peak width at half maximum of less than 0.30° in a powder X-ray diffraction pattern where the diffraction intensity is maximum.
前記化学機械研磨用組成物の一態様において、
前記（Ａ１）アルミナ含有粒子のＳｉ含有割合が１～４０ｗｔ・ｐｐｍであることができる。
In one embodiment of the chemical mechanical polishing composition,
The Si content of the alumina-containing particles (A1) may be 1 to 40 wt·ppm.
前記化学機械研磨用組成物のいずれかの態様において、
前記（Ｂ）有機酸が、一分子内に、ヒドロキシル基を０～１個及びカルボキシル基を１～２個有し、かつ、第一酸解離定数ｐＫａが１．５～４．５であることができる。
In any embodiment of the chemical mechanical polishing composition,
The organic acid (B) has 0 to 1 hydroxyl group and 1 to 2 carboxyl groups in one molecule, and has a primary acid dissociation constant pKa of 1.5 to 4.5. I can do it.
前記化学機械研磨用組成物のいずれかの態様において、
前記（Ｂ）有機酸が、マレイン酸、コハク酸、乳酸、マロン酸、ｐ－ヒドロキシ安息香酸、ラウリン酸及びグリコール酸よりなる群から選ばれる少なくとも１種であることができる。
In any embodiment of the chemical mechanical polishing composition,
The organic acid (B) can be at least one selected from the group consisting of maleic acid, succinic acid, lactic acid, malonic acid, p-hydroxybenzoic acid, lauric acid, and glycolic acid.
前記化学機械研磨用組成物のいずれかの態様において、
前記（Ａ１）アルミナ含有粒子の比重が４．０以上であることができる。
In any embodiment of the chemical mechanical polishing composition,
The specific gravity of the alumina-containing particles (A1) can be 4.0 or more.
本発明に係る化学機械研磨方法の一態様は、
前記いずれかの態様の化学機械研磨用組成物を用いて、樹脂を含有する被研磨面を研磨する工程を含む。
One aspect of the chemical mechanical polishing method according to the present invention is
The method includes a step of polishing a surface to be polished containing resin using the chemical mechanical polishing composition of any of the above embodiments.
本発明に係る化学機械研磨方法の一態様は、
前記いずれかの態様の化学機械研磨用組成物を用いて、樹脂及び配線金属を含有する被研磨面を研磨する工程を含む。
One aspect of the chemical mechanical polishing method according to the present invention is
The method includes a step of polishing a surface to be polished containing a resin and a wiring metal using the chemical mechanical polishing composition of any of the above embodiments.
本発明に係る化学機械研磨方法の一態様は、
（Ａ１）アルミナ含有粒子を含有する第１化学機械研磨用組成物を使用して樹脂を含有する被研磨面を研磨する第１研磨工程と、
前記第１研磨工程後の被研磨面を、さらに（Ａ２）シリカ粒子を含有する第２化学機械研磨用組成物を使用して研磨する第２研磨工程と、
を含み、
前記（Ａ１）アルミナ含有粒子が、粉末Ｘ線回折パターンにおける回折強度が最大となるピーク部分の半値幅が０．３０°未満のものである。
One aspect of the chemical mechanical polishing method according to the present invention is
(A1) a first polishing step of polishing a surface to be polished containing resin using a first chemical mechanical polishing composition containing alumina-containing particles;
A second polishing step of polishing the surface to be polished after the first polishing step using a second chemical mechanical polishing composition containing (A2) silica particles;
including;
The alumina-containing particles (A1) have a peak width at half maximum of less than 0.30° in a powder X-ray diffraction pattern where the diffraction intensity is maximum.
前記化学機械研磨方法の一態様において、
前記（Ａ１）アルミナ含有粒子のＳｉ含有割合が１～４０ｗｔ・ｐｐｍであることができる。
In one aspect of the chemical mechanical polishing method,
The Si content of the alumina-containing particles (A1) may be 1 to 40 wt·ppm.
前記化学機械研磨方法のいずれかの態様において、
前記（Ａ１）アルミナ含有粒子の比重が４．０以上であることができる。
In any aspect of the chemical mechanical polishing method,
The specific gravity of the alumina-containing particles (A1) can be 4.0 or more.
前記化学機械研磨方法のいずれかの態様において、
前記第１化学機械研磨用組成物及び前記第２化学機械研磨用組成物のうち少なくとも一方が（Ｂ）有機酸をさらに含有することができる。
In any aspect of the chemical mechanical polishing method,
At least one of the first chemical mechanical polishing composition and the second chemical mechanical polishing composition may further contain (B) an organic acid.
前記化学機械研磨方法のいずれかの態様において、
前記（Ｂ）有機酸が、一分子内に、ヒドロキシル基を０～１個及びカルボキシル基を１
～２個有し、かつ、第一酸解離定数ｐＫａが１．５～４．５であることができる。
In any aspect of the chemical mechanical polishing method,
The organic acid (B) has 0 to 1 hydroxyl group and 1 carboxyl group in one molecule.
2, and a primary acid dissociation constant pKa of 1.5 to 4.5.
前記化学機械研磨方法のいずれかの態様において、
前記（Ｂ）有機酸が、マレイン酸、コハク酸、乳酸、マロン酸、ｐ－ヒドロキシ安息香酸、ラウリン酸及びグリコール酸よりなる群から選ばれる少なくとも１種であることができる。
In any aspect of the chemical mechanical polishing method,
The organic acid (B) can be at least one selected from the group consisting of maleic acid, succinic acid, lactic acid, malonic acid, p-hydroxybenzoic acid, lauric acid, and glycolic acid.
本発明に係る化学機械研磨用組成物によれば、配線金属及び樹脂膜を有する回路基板を化学機械研磨する際に、樹脂膜に対する研磨速度が十分に高く、かつ、被研磨面を高平坦化することができる。 According to the chemical-mechanical polishing composition of the present invention, when chemical-mechanically polishing a circuit board having wiring metal and a resin film, the polishing rate for the resin film is sufficiently high and the surface to be polished is highly flattened. can do.
本発明に係る化学機械研磨方法によれば、配線金属及び樹脂膜を有する回路基板を化学機械研磨する際に、樹脂膜に対する研磨速度が十分に高いため高スループットで研磨することができ、不要な樹脂膜を研磨除去した後に表出する配線金属／樹脂膜が共存する被研磨面において、高平坦化及びスクラッチ発生の低減を実現できる。 According to the chemical-mechanical polishing method of the present invention, when chemical-mechanically polishing a circuit board having wiring metal and a resin film, the polishing rate for the resin film is sufficiently high, so polishing can be performed with high throughput, and unnecessary It is possible to achieve high flatness and a reduction in the occurrence of scratches on the polished surface where the wiring metal/resin film coexists, which is exposed after the resin film is removed by polishing.
以下、本発明の好適な実施形態について詳細に説明する。なお、本発明は、下記の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において実施される各種の変形例も含む。 Hereinafter, preferred embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, but also includes various modifications that may be implemented within the scope of not changing the gist of the present invention.
本明細書において、「～」を用いて記載された数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む意味である。 In this specification, a numerical range described using "~" means that the numerical values described before and after "~" are included as lower and upper limits.
本発明では、第１研磨工程に使用される化学機械研磨用組成物を「第１化学機械研磨用組成物」と定義し、第２研磨工程に使用される化学機械研磨用組成物を「第２化学機械研磨用組成物」と定義する。 In the present invention, the chemical mechanical polishing composition used in the first polishing step is defined as the "first chemical mechanical polishing composition", and the chemical mechanical polishing composition used in the second polishing step is defined as the "first chemical mechanical polishing composition". 2 chemical mechanical polishing composition.
本発明における「樹脂」とは、回路基板を作成するのに使用される樹脂であれば特に制限されるものではないが、例えば、ポリイミド系、フェノール系、エポキシ系、メラミン系、尿素系、不飽和ポリエステル系、ジアリルフタレート系、ポリウレタン系、シリコン系、その他の熱硬化性樹脂、およびノボラック等の熱可塑性樹脂を架橋剤によって硬化させた架橋型硬化性樹脂等が挙げられる。これらの硬化性樹脂の具体例としては、環化ゴム－ビスアジド系、ＤＮＱ－ノボラック樹脂系、化学増幅型樹脂系、ポリヒドロキシスチレン、ポリメチルメタクリレート、フッ素樹脂等の感光性樹脂等が挙げられる。 The "resin" in the present invention is not particularly limited as long as it is a resin used to create a circuit board, but includes, for example, polyimide, phenol, epoxy, melamine, urea, and non-resin. Examples include saturated polyester-based, diallylphthalate-based, polyurethane-based, silicone-based, other thermosetting resins, and crosslinked curable resins obtained by curing thermoplastic resins such as novolak with a crosslinking agent. Specific examples of these curable resins include cyclized rubber-bisazide systems, DNQ-novolak resin systems, chemically amplified resin systems, and photosensitive resins such as polyhydroxystyrene, polymethyl methacrylate, and fluororesins.
本発明における「配線金属」とは、回路基板の配線を作成するのに使用される金属であ
れば特に制限されるものではないが、例えば、アルミニウム、銅、及びこれらの合金が挙げられる。
The "wiring metal" in the present invention is not particularly limited as long as it is a metal used to create wiring on a circuit board, and examples thereof include aluminum, copper, and alloys thereof.
１．化学機械研磨方法
本実施形態に係る化学機械研磨方法は、（Ａ１）アルミナ含有粒子を含有する第１化学機械研磨用組成物を使用して樹脂を含有する被研磨面を研磨する第１研磨工程と、前記第１研磨工程後の被研磨面を、さらに（Ａ２）シリカ粒子を含有する第２化学機械研磨用組成物を使用して研磨する第２研磨工程と、を含み、前記（Ａ１）アルミナ含有粒子が、粉末Ｘ線回折パターンにおける回折強度が最大となるピーク部分の半値幅が０．３０°未満のものである。
1. Chemical mechanical polishing method The chemical mechanical polishing method according to the present embodiment includes (A1) a first polishing step of polishing a surface to be polished containing resin using a first chemical mechanical polishing composition containing alumina-containing particles; and a second polishing step of polishing the surface to be polished after the first polishing step using a second chemical mechanical polishing composition containing (A2) silica particles; The alumina-containing particles have a peak width at half maximum of less than 0.30° in a powder X-ray diffraction pattern where the diffraction intensity is maximum.
図１は、本実施形態に係る化学機械研磨方法の使用に適した被処理体を模式的に示した断面図である。本実施形態に係る化学機械研磨方法は、回路基板を作成する際に広く適用することができるが、図１に示すような、金属配線パターンが形成された配線金属１０上に樹脂膜１２が多く存在する被処理体１００から回路基板を作成する用途に好適である。 FIG. 1 is a cross-sectional view schematically showing an object to be processed suitable for use in the chemical mechanical polishing method according to the present embodiment. The chemical mechanical polishing method according to the present embodiment can be widely applied when creating circuit boards, but as shown in FIG. This is suitable for use in creating a circuit board from an existing object to be processed 100.
第１化学機械研磨用組成物に含有される（Ａ１）アルミナ含有粒子は、樹脂膜を研磨するのに適した硬度を有している。そのため、第１化学機械研磨用組成物は、樹脂膜に対する研磨速度が十分に高く、配線金属１０上に多く存在する樹脂膜１２を粗方研磨する用途に適している。
The alumina-containing particles (A1) contained in the first chemical mechanical polishing composition have hardness suitable for polishing a resin film. Therefore, the first chemical mechanical polishing composition has a sufficiently high polishing rate for the resin film, and is suitable for rough polishing the
その一方で、第１化学機械研磨用組成物に含有される（Ａ１）アルミナ含有粒子は、銅または銅合金などの柔らかい配線金属を過剰に研磨してしまう傾向がある。そのため、第１化学機械研磨用組成物を用いて配線金属／樹脂膜が共存する被研磨面を研磨すると、被研磨面の平坦性が損なわれやすく、また配線金属上にスクラッチ（研磨傷）が発生しやすい。 On the other hand, the alumina-containing particles (A1) contained in the first chemical mechanical polishing composition tend to excessively polish soft wiring metals such as copper or copper alloy. Therefore, when the first chemical mechanical polishing composition is used to polish a polished surface on which wiring metal/resin film coexists, the flatness of the polished surface is likely to be impaired, and scratches (polishing scratches) may occur on the wiring metal. Likely to happen.
第２化学機械研磨用組成物に含有される（Ａ２）シリカ粒子は、（Ａ１）アルミナ含有粒子よりも硬度が低く、配線金属を研磨する用途に適している。そのため、第２化学機械研磨用組成物は、配線金属や樹脂膜に対する研磨速度が第１化学機械研磨用組成物に比べて低いものの、配線金属／樹脂膜が共存する被研磨面において精密かつスクラッチの発生が低減された研磨を実現することができる。 The silica particles (A2) contained in the second chemical mechanical polishing composition have lower hardness than the alumina-containing particles (A1), and are suitable for polishing wiring metal. Therefore, although the second chemical-mechanical polishing composition has a lower polishing rate for wiring metal and resin films than the first chemical-mechanical polishing composition, it can produce precision and scratches on the surface to be polished where wiring metal/resin films coexist. It is possible to achieve polishing with reduced occurrence of.
したがって、第１研磨工程において、第１化学機械研磨用組成物を用いて配線金属１０上に多く存在する樹脂膜１２（図１参照）を粗方研磨した後、第２研磨工程において、第２化学機械研磨用組成物を用いて配線金属／樹脂膜が共存する被研磨面（図２参照）を研磨することによって、高平坦化され、かつ、スクラッチの発生が低減された回路基板（図３参照）が得られる。
Therefore, in the first polishing step, after roughly polishing the resin film 12 (see FIG. 1) which is present in large amount on the
本実施形態に係る化学機械研磨方法は、上述の第１化学機械研磨用組成物を用いて樹脂膜を研磨するため、その研磨速度が大きく、また上述の第２化学機械研磨用組成物を用いて配線金属／樹脂膜が共存する被研磨面を研磨するため、面内平坦性が良好となり、ディッシング等が生じにくい。 The chemical-mechanical polishing method according to the present embodiment polishes a resin film using the first chemical-mechanical polishing composition described above, so the polishing rate is high, and the chemical-mechanical polishing method uses the second chemical-mechanical polishing composition described above. Since the surface to be polished where the wiring metal/resin film coexists is polished, the in-plane flatness is good and dishing etc. are less likely to occur.
また、本実施形態に係る化学機械研磨方法によって製造された回路基板は、面内平坦性が高く、ディッシング等が生じにくいため、該回路基板を積層して形成される多層回路基板も、基板全体にわたって均一な厚みを有し、かつ、平坦な表面を有するものとなる。 Furthermore, since the circuit board manufactured by the chemical mechanical polishing method according to the present embodiment has high in-plane flatness and is less prone to dishing, the multilayer circuit board formed by stacking the circuit boards can also be It has a uniform thickness and a flat surface.
以下、本実施形態に係る化学機械研磨方法を構成する各工程について詳細に説明する。 Each step constituting the chemical mechanical polishing method according to this embodiment will be described in detail below.
１．１．第１研磨工程
第１研磨工程は、第１化学機械研磨用組成物を使用して、例えば図１に示すような樹脂膜を含有する被研磨面を研磨する工程である。第１化学機械研磨用組成物に含有される（Ａ１）アルミナ含有粒子は、樹脂膜を研磨するのに適した硬度を有している。そのため、第１化学機械研磨用組成物は、樹脂膜に対する研磨速度が十分に高く、樹脂膜を粗方研磨する用途に適している。
1.1. First Polishing Step The first polishing step is a step of polishing a polished surface containing a resin film as shown in FIG. 1, for example, using the first chemical mechanical polishing composition. The alumina-containing particles (A1) contained in the first chemical mechanical polishing composition have hardness suitable for polishing a resin film. Therefore, the first chemical mechanical polishing composition has a sufficiently high polishing rate for resin films, and is suitable for rough polishing of resin films.
１．１．１．第１化学機械研磨用組成物
＜（Ａ１）アルミナ含有粒子＞
第１化学機械研磨用組成物は、（Ａ１）アルミナ含有粒子を含有する。本発明における「（Ａ１）アルミナ含有粒子」は、アルミナ（Ａｌ２Ｏ３）のみから形成される粒子であってもよいし、アルミナ以外の他の化合物を含有する粒子であってもよい。（Ａ１）アルミナ含有粒子がアルミナ以外の他の化合物を含有する粒子である場合、（Ａ１）アルミナ含有粒子の一粒子中のアルミナの質量が５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが特に好ましい。（Ａ１）アルミナ含有粒子中のアルミナの含有量が前記範囲にあると、樹脂膜を研磨するのに適した硬度となるため、樹脂膜を高速研磨することができる。
1.1.1. First chemical mechanical polishing composition <(A1) Alumina-containing particles>
The first chemical mechanical polishing composition contains (A1) alumina-containing particles. The "(A1) alumina-containing particles" in the present invention may be particles formed only from alumina (Al 2 O 3 ), or may be particles containing other compounds other than alumina. (A1) When the alumina-containing particles are particles containing a compound other than alumina, the mass of alumina in each particle of the (A1) alumina-containing particles is preferably 50% by mass or more, and preferably 70% by mass or more. It is more preferable that it is, and it is especially preferable that it is 80 mass % or more. (A1) When the content of alumina in the alumina-containing particles is within the above range, the hardness is suitable for polishing the resin film, so that the resin film can be polished at high speed.
一般的に、結晶性のアルミナ粒子の粉末Ｘ線回折パターンでは、入射角が２５°以上７５°以下の範囲内において回折強度が最大となるピークを有する。第１化学機械研磨用組成物に含有される（Ａ１）アルミナ含有粒子は、粉末Ｘ線回折パターンにおける回折強度が最大となるピーク部分の半値幅が０．３０°未満であり、好ましくは０．１５°以上０．２９°以下であり、より好ましくは０．１８°以上０．２８°以下であり、特に好ましくは０．２０°以上０．２７°以下である。当該半値幅が前記範囲にある（Ａ１）アルミナ含有粒子は、結晶子が均質となり、樹脂膜を研磨するのに適した硬度となる。そのため、第１化学機械研磨用組成物を用いることにより、膜厚の厚い樹脂膜を有する回路基板の樹脂膜を高速研磨することができる。 Generally, a powder X-ray diffraction pattern of crystalline alumina particles has a peak in which the diffraction intensity is maximum at an incident angle of 25° or more and 75° or less. The alumina-containing particles (A1) contained in the first chemical mechanical polishing composition have a peak width at half maximum of less than 0.30°, where the diffraction intensity is maximum in a powder X-ray diffraction pattern, and preferably 0.30°. The angle is 15° or more and 0.29° or less, more preferably 0.18° or more and 0.28° or less, particularly preferably 0.20° or more and 0.27° or less. The alumina-containing particles (A1) whose half-value width is within the above range have homogeneous crystallites and have a hardness suitable for polishing a resin film. Therefore, by using the first chemical mechanical polishing composition, the resin film of a circuit board having a thick resin film can be polished at high speed.
なお、粉末Ｘ線回折パターンとは、Ｘ線源としてＣｕＫα線を用いた粉体Ｘ線回折による試料測定を行った際の、入射角を横軸、回折強度を縦軸とする２次元グラフにおける、各入射角で測定される回折強度のプロット線のことを指す。 Note that a powder X-ray diffraction pattern is a two-dimensional graph in which the horizontal axis is the incident angle and the vertical axis is the diffraction intensity when a sample is measured by powder X-ray diffraction using CuKα rays as an X-ray source. , refers to the plot line of the diffraction intensity measured at each incident angle.
（Ａ１）アルミナ含有粒子の平均一次粒子径は、好ましくは０．１～５．０μｍであり、より好ましくは０．３～４．０μｍであり、特に好ましくは０．４～３．５μｍである。前記範囲の平均一次粒子径を有する（Ａ１）アルミナ含有粒子であれば、樹脂膜に対する十分な研磨速度が得られると共に、粒子の沈降・分離を生ずることのない安定性に優れた化学機械研磨用組成物が得られるため、良好な研磨特性が得られる。 (A1) The average primary particle diameter of the alumina-containing particles is preferably 0.1 to 5.0 μm, more preferably 0.3 to 4.0 μm, and particularly preferably 0.4 to 3.5 μm. . Alumina-containing particles (A1) having an average primary particle diameter within the above range can provide a sufficient polishing rate for resin films, and are highly stable for chemical mechanical polishing without sedimentation or separation of particles. Since a composition is obtained, good polishing properties can be obtained.
なお、（Ａ１）アルミナ含有粒子の平均一次粒子径は、原料となる（Ａ１）アルミナ含有粒子（分散体）の一部を乾燥させて得られた試料について、例えば流動式比表面積自動測定装置（株式会社島津製作所製、「ｍｉｃｒｏｍｅｔｒｉｃｓ ＦｌｏｗＳｏｒｂＩＩ２３００」）を用いてＢＥＴ法による比表面積を測定し、その測定値から算出して求めることができる。 The average primary particle diameter of the (A1) alumina-containing particles is measured using, for example, a fluidized specific surface area automatic measuring device ( The specific surface area can be determined by measuring the specific surface area by the BET method using "micrometrics FlowSorb II 2300" (manufactured by Shimadzu Corporation) and calculating from the measured value.
（Ａ１）アルミナ含有粒子の長径（Ｒｍａｘ）と短径（Ｒｍｉｎ）との比率（Ｒｍａｘ／Ｒｍｉｎ）は、好ましくは１．１０以上１．８０以下であり、より好ましくは１．１５以上１．６０以下であり、特に好ましくは１．２０以上１．５０以下である。比率（Ｒｍａｘ／Ｒｍｉｎ）が前記範囲にあると、（Ａ１）アルミナ含有粒子と被研磨面との引っ掛かり及び摩擦力が適度となるため、スクラッチ等の欠陥を低減しながら、樹脂膜に対する高研磨速度と被研磨面の高平坦化を両立させることができる。 (A1) The ratio (Rmax/Rmin) between the major axis (Rmax) and the minor axis (Rmin) of the alumina-containing particles is preferably 1.10 or more and 1.80 or less, more preferably 1.15 or more and 1.60. It is below, particularly preferably 1.20 or more and 1.50 or less. When the ratio (Rmax/Rmin) is within the above range, (A1) the catching and frictional force between the alumina-containing particles and the surface to be polished will be moderate, so a high polishing rate for the resin film can be achieved while reducing defects such as scratches. It is possible to achieve both high flatness of the surface to be polished.
ここで、（Ａ１）アルミナ含有粒子の長径（Ｒｍａｘ）とは、透過型電子顕微鏡により撮影された一つの独立した（Ａ１）アルミナ含有粒子の像について、像の端部と端部を結んだ距離のうち最も長い距離を意味する。（Ａ１）アルミナ含有粒子の短径（Ｒｍｉｎ）とは、透過型電子顕微鏡により撮影された一つの独立した（Ａ１）アルミナ含有粒子の像について、像の端部と端部を結んだ距離のうち最も短い距離を意味する。 Here, the major axis (Rmax) of the (A1) alumina-containing particles is the distance between the edges of one independent image of the (A1) alumina-containing particles taken by a transmission electron microscope. means the longest distance. The minor axis (Rmin) of the (A1) alumina-containing particles is the distance between the edges of one independent image of the (A1) alumina-containing particles taken with a transmission electron microscope. means the shortest distance.
（Ａ１）アルミナ含有粒子の長径（Ｒｍａｘ）及び短径（Ｒｍｉｎ）は、以下のようにして測定することができる。例えば、図４に示すように透過型電子顕微鏡により撮影された一つの独立したアルミナ含有粒子１の像が楕円形状である場合、楕円形状の長軸ａをアルミナ含有粒子１の長径（Ｒｍａｘ）と判別し、楕円形状の短軸ｂをアルミナ含有粒子１の短径（Ｒｍｉｎ）と判別する。長径と短径との比率（Ｒｍａｘ／Ｒｍｉｎ）は、このような判別手法により５０個のアルミナ含有粒子の長径（Ｒｍａｘ）及び短径（Ｒｍｉｎ）を測定し、長径（Ｒｍａｘ）及び短径（Ｒｍｉｎ）の平均値を算出した後、長径と短径との比率（Ｒｍａｘ／Ｒｍｉｎ）を計算して求めることができる。 (A1) The major axis (Rmax) and minor axis (Rmin) of the alumina-containing particles can be measured as follows. For example, if the image of one independent alumina-containing particle 1 taken by a transmission electron microscope is elliptical as shown in FIG. The short axis b of the elliptical shape is determined to be the short axis (Rmin) of the alumina-containing particles 1. The ratio of the major axis to the minor axis (Rmax/Rmin) is determined by measuring the major axis (Rmax) and the minor axis (Rmin) of 50 alumina-containing particles using such a discrimination method, and then determining the major axis (Rmax) and the minor axis (Rmin). ) can be determined by calculating the ratio of the major axis to the minor axis (Rmax/Rmin).
（Ａ１）アルミナ含有粒子の真比重は、好ましくは４．０以上であり、より好ましくは４．３以上である。（Ａ１）アルミナ含有粒子の真比重が前記値以上であれば、研磨時にかかる応力が均一となる結果、研磨後の被研磨面の平坦性が向上する。また、（Ａ１）アルミナ含有粒子の真比重は、好ましくは６．０以下であり、より好ましくは５．０以下である。（Ａ１）アルミナ含有粒子の真比重が前記値以下であれば、第１化学機械研磨用組成物中の粒子の沈降・分離を抑制することができる。（Ａ１）アルミナ含有粒子の真比重は、ＪＩＳ ９３０１－２－１：１９９９に記載されている「ピクノメーター法による真密度」測定法に準じて測定することができる。 (A1) The true specific gravity of the alumina-containing particles is preferably 4.0 or more, more preferably 4.3 or more. (A1) If the true specific gravity of the alumina-containing particles is equal to or higher than the above value, the stress applied during polishing becomes uniform, and as a result, the flatness of the polished surface after polishing improves. Further, the true specific gravity of the alumina-containing particles (A1) is preferably 6.0 or less, more preferably 5.0 or less. (A1) If the true specific gravity of the alumina-containing particles is equal to or less than the above value, sedimentation and separation of particles in the first chemical mechanical polishing composition can be suppressed. (A1) The true specific gravity of the alumina-containing particles can be measured according to the "true density by pycnometer method" measurement method described in JIS 9301-2-1:1999.
（Ａ１）アルミナ含有粒子は、アルミナ以外の他の化合物を含有する粒子であってもよい。このような他の化合物としては、ＳｉＣ、ＳｉＣｌ２、ＳｉＣｌ４、ＳｉＢｒ２、ＳｉＢｒ４、ＳｉＦ２、ＳｉＦ４、ＳｉＯ、ＳｉＯ２、ＳｉＨ４、Ｓｉ２Ｈ６、Ｈ２ＳｉＯ３、Ｈ４ＳｉＯ４、Ｓｉ（ＣＨ３）４、Ｓｉ（Ｃ２Ｈ５）２等のＳｉ含有化合物、ＴｉＯ２、Ｆｅ２Ｏ３、Ｎａ２Ｏ等が挙げられる。これらの中でも、（Ａ１）アルミナ含有粒子の表面酸性をシラノール基によりコントロールでき、配線金属との適度なケミカル親和性を容易に発現できることから、ＳｉＯ２であることが好ましい。 (A1) The alumina-containing particles may be particles containing a compound other than alumina. Such other compounds include SiC, SiCl2 , SiCl4 , SiBr2, SiBr4 , SiF2 , SiF4 , SiO, SiO2 , SiH4 , Si2H6 , H2SiO3 , H4SiO 4 , Si(CH 3 ) 4 , Si(C 2 H 5 ) 2 and other Si-containing compounds, TiO 2 , Fe 2 O 3 , Na 2 O, and the like. Among these, SiO 2 is preferred because (A1) the surface acidity of the alumina-containing particles can be controlled by the silanol group and it can easily develop an appropriate chemical affinity with the wiring metal.
（Ａ１）アルミナ含有粒子がＳｉ含有化合物を含有する場合、（Ａ１）アルミナ含有粒子中のＳｉ含有割合は、好ましくは１～４０ｗｔ・ｐｐｍであり、より好ましくは３～３０ｗｔ・ｐｐｍであり、特に好ましくは１０～２５ｗｔ・ｐｐｍである。（Ａ１）アルミナ含有粒子中のＳｉ含有割合が１ｗｔ・ｐｐｍ以上であると、Ｓｉ含有化合物に含まれるＳｉ原子と配線表面との間に化学的親和性が生じるため、（Ａ１）アルミナ含有粒子による過剰研磨が抑制され、配線金属と樹脂膜が共存する被研磨面においても平坦性が向上する。一方、（Ａ１）アルミナ含有粒子中のＳｉ含有割合が４０ｗｔ・ｐｐｍ以下であると、（Ａ１）アルミナ含有粒子が研磨に適した硬度となり、樹脂膜を高速研磨することができる。すなわち、本実施形態における（Ａ１）アルミナ含有粒子中のＳｉ含有割合が１～４０ｗｔ・ｐｐｍであれば、樹脂膜を高速で研磨することができ、かつ、研磨後の被研磨面の平坦性が向上する。 (A1) When the alumina-containing particles contain a Si-containing compound, the Si content in the alumina-containing particles (A1) is preferably 1 to 40 wt·ppm, more preferably 3 to 30 wt·ppm, and particularly Preferably it is 10 to 25 wt·ppm. (A1) If the Si content in the alumina-containing particles is 1 wt ppm or more, chemical affinity will occur between the Si atoms contained in the Si-containing compound and the wiring surface. Excessive polishing is suppressed and flatness is improved even on the surface to be polished where wiring metal and resin film coexist. On the other hand, when the Si content in the alumina-containing particles (A1) is 40 wt·ppm or less, the alumina-containing particles (A1) have a hardness suitable for polishing, and the resin film can be polished at high speed. That is, if the Si content in the alumina-containing particles (A1) in this embodiment is 1 to 40 wt·ppm, the resin film can be polished at high speed, and the flatness of the polished surface after polishing can be improved. improves.
（Ａ１）アルミナ含有粒子中のＳｉ含有量は、ＪＩＳ Ｒ１６４９：２００２に記載されている測定法に準じて測定することができる。具体的には、試料となる（Ａ１）アルミナ含有粒子に硫酸を加えて加圧分解容器中で加熱して溶解し試料溶液を調製し、その溶液をＩＣＰ発光分光分析装置のアルゴンプラズマ中に噴霧し、Ｓｉの発光強度を測定することにより、（Ａ）アルミナ含有粒子中のＳｉ含有量を求める。 (A1) The Si content in the alumina-containing particles can be measured according to the measuring method described in JIS R1649:2002. Specifically, a sample solution is prepared by adding sulfuric acid to alumina-containing particles (A1), which is a sample, and dissolving them by heating in a pressure decomposition container, and then spraying the solution into argon plasma of an ICP emission spectrometer. Then, by measuring the luminescence intensity of Si, the Si content in the alumina-containing particles (A) is determined.
（Ａ１）アルミナ含有粒子の含有量は、第１化学機械研磨用組成物の全質量に対して、０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上が特に好ましい。（Ａ１）アルミナ含有粒子の含有量が前記範囲である場合、樹脂膜をより高速で研磨することができる。（Ａ１）アルミナ含有粒子の含有量は、１５質量％以下が好ましく、１０質量％以下がより好ましく、８質量％以下が特に好ましい。（Ａ１）アルミナ含有粒子の含有量が前記範囲である場合、被研磨面の研磨傷の発生をより低減することができる。 (A1) The content of the alumina-containing particles is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 0.5% by mass with respect to the total mass of the first chemical mechanical polishing composition. The above is particularly preferable. (A1) When the content of the alumina-containing particles is within the above range, the resin film can be polished at a higher speed. (A1) The content of the alumina-containing particles is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 8% by mass or less. (A1) When the content of the alumina-containing particles is within the above range, the occurrence of polishing scratches on the surface to be polished can be further reduced.
＜その他の添加剤＞
第１化学機械研磨用組成物は、主要な液状媒体である水の他、必要に応じて、（Ｂ）有機酸、酸化剤、界面活性剤、含窒素複素環化合物、無機酸及びその塩、水溶性高分子等を含有してもよい。
<Other additives>
In addition to water as the main liquid medium, the first chemical mechanical polishing composition optionally contains (B) an organic acid, an oxidizing agent, a surfactant, a nitrogen-containing heterocyclic compound, an inorganic acid and its salt, It may also contain water-soluble polymers and the like.
・水
第１化学機械研磨用組成物は、水を主要な液状媒体として含有する。第１化学機械研磨用組成物を調製する際に添加し得る水としては、特に制限されるものではないが、純水が好ましい。水は、上述した第１化学機械研磨用組成物の構成材料の残部として配合されていればよく、水の含有量については特に制限はない。
- Water The first chemical mechanical polishing composition contains water as the main liquid medium. The water that can be added when preparing the first chemical mechanical polishing composition is not particularly limited, but pure water is preferable. Water may be blended as the remainder of the constituent materials of the first chemical mechanical polishing composition described above, and there is no particular restriction on the water content.
・（Ｂ）有機酸
第１化学機械研磨用組成物は、（Ｂ）有機酸を含有することが好ましい。（Ｂ）有機酸の機能としては、樹脂膜及び配線金属に対する研磨速度を向上させて、配線金属を含む被研磨面の研磨中における金属塩の析出を抑制することが挙げられる。
- (B) Organic acid The first chemical mechanical polishing composition preferably contains (B) an organic acid. (B) The function of the organic acid is to improve the polishing rate for the resin film and the wiring metal, and to suppress the precipitation of metal salts during polishing of the surface to be polished including the wiring metal.
（Ｂ）有機酸としては、配線金属の元素からなるイオンまたは原子に対して配位能力を有する有機酸であることが好ましい。このような有機酸としては、一分子内にヒドロキシル基を０～１個及びカルボキシル基を１～２個有する有機酸がより好ましく、一分子内にヒドロキシル基を０～１個及びカルボキシル基を１～２個有し、かつ、第一酸解離定数ｐＫａが１．５～４．５である有機酸がさらにより好ましく、一分子内にヒドロキシル基及びカルボキシル基を合計２個以上有し、かつ、第一酸解離定数ｐＫａが１．５～４．５である有機酸が特に好ましい。このような（Ｂ）有機酸であれば、配線金属等の表面に対する配位能力が高いので、配線金属に対する研磨速度を向上させることができる場合がある。また、このような（Ｂ）有機酸は、配線金属の研磨により発生する金属イオンを安定化し、金属塩の析出を抑制することができるので、被研磨面の表面荒れを抑制しながら高度な平坦性が得られるとともに、配線の研磨傷の発生を低減することができる場合がある。なお、これらの（Ｂ）有機酸は、銅又は銅合金への配位能力が特に高いため、配線金属が銅又は銅合金の場合に好適となる。 (B) The organic acid is preferably an organic acid that has the ability to coordinate with ions or atoms of the elements of the wiring metal. As such an organic acid, an organic acid having 0 to 1 hydroxyl group and 1 to 2 carboxyl groups in one molecule is more preferable, and one having 0 to 1 hydroxyl group and 1 carboxyl group in one molecule. Even more preferred is an organic acid having 2 or more hydroxyl groups and a carboxyl group in one molecule, and a first acid dissociation constant pKa of 1.5 to 4.5, and having a total of 2 or more hydroxyl groups and carboxyl groups in one molecule, and Particularly preferred are organic acids having a primary acid dissociation constant pKa of 1.5 to 4.5. Since such an organic acid (B) has a high ability to coordinate with the surface of wiring metal, etc., it may be possible to improve the polishing rate for wiring metal. In addition, such an organic acid (B) can stabilize the metal ions generated by polishing the wiring metal and suppress the precipitation of metal salts, so it can suppress the surface roughness of the polished surface and achieve a high level of flatness. In some cases, it is possible to reduce the occurrence of polishing scratches on wiring. Note that these (B) organic acids have particularly high coordination ability to copper or copper alloys, and therefore are suitable when the wiring metal is copper or copper alloys.
（Ｂ）有機酸の具体例としては、乳酸、酒石酸、フマル酸、グリコール酸、フタル酸、マレイン酸、ギ酸、酢酸、シュウ酸、クエン酸、リンゴ酸、マロン酸、グルタル酸、コハク酸、安息香酸、ｐ－ヒドロキシ安息香酸、ラウリン酸、キノリン酸、キナルジン酸、アミド硫酸；グリシン、アラニン、アスパラギン酸、グルタミン酸、リシン、アルギニン、トリプトファン、芳香族アミノ酸、及び複素環型アミノ酸等のアミノ酸が挙げられる。これらの中でも、マレイン酸、コハク酸、乳酸、マロン酸、ｐ－ヒドロキシ安息香酸、ラウリン酸及びグリコール酸よりなる群から選ばれる少なくとも１種であることが好ましい。（Ｂ）有機酸は、１種単独で用いてもよいし、任意の割合で２種以上を組み合わせて用いてもよい。 (B) Specific examples of organic acids include lactic acid, tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid, acetic acid, oxalic acid, citric acid, malic acid, malonic acid, glutaric acid, succinic acid, and benzoic acid. amino acids such as p-hydroxybenzoic acid, lauric acid, quinolinic acid, quinaldic acid, amidosulfuric acid; glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, tryptophan, aromatic amino acids, and heterocyclic amino acids. . Among these, at least one selected from the group consisting of maleic acid, succinic acid, lactic acid, malonic acid, p-hydroxybenzoic acid, lauric acid, and glycolic acid is preferred. (B) Organic acids may be used alone or in combination of two or more in any proportion.
また、（Ｂ）有機酸は、上記有機酸の塩であってもよく、化学機械研磨用組成物中で別
途添加した塩基と反応して上記有機酸の塩となっていてもよい。このような塩基としては、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等のアルカリ金属の水酸化物、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリン等の有機アルカリ化合物、及びアンモニア等が挙げられる。
Moreover, the organic acid (B) may be a salt of the above-mentioned organic acid, or may react with a base added separately in the chemical mechanical polishing composition to become a salt of the above-mentioned organic acid. Examples of such bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, organic alkali compounds such as tetramethylammonium hydroxide (TMAH), choline, and ammonia. can be mentioned.
（Ｂ）有機酸の含有量は、化学機械研磨用組成物の全質量に対して、０．００１～１質量％が好ましく、０．０１～０．１質量％がより好ましい。（Ｂ）有機酸の含有量が前記範囲であると、樹脂膜及び配線金属に対する研磨速度と平坦性が向上する場合がある。 The content of the organic acid (B) is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.1% by mass, based on the total mass of the chemical mechanical polishing composition. (B) When the content of the organic acid is within the above range, the polishing rate and flatness of the resin film and wiring metal may be improved.
・酸化剤
第１化学機械研磨用組成物は、酸化剤を含有してもよい。酸化剤を含有することにより、樹脂膜や配線金属を酸化して研磨液成分との錯化反応を促すことにより、被研磨面に脆弱な改質層を作り出すことができるため、良好な研磨特性が得られる場合がある。
- Oxidizing agent The first chemical mechanical polishing composition may contain an oxidizing agent. Containing an oxidizing agent oxidizes the resin film and wiring metal and promotes a complex reaction with the polishing liquid components, creating a brittle modified layer on the polished surface, resulting in good polishing properties. may be obtained.
酸化剤としては、例えば、過硫酸アンモニウム、過硫酸カリウム、過酸化水素、硝酸第二鉄、硝酸二アンモニウムセリウム、次亜塩素酸カリウム、オゾン、過ヨウ素酸カリウム、過酢酸等が挙げられる。これらの酸化剤のうち、過ヨウ素酸カリウム、次亜塩素酸カリウム及び過酸化水素から選択される少なくとも１種が好ましく、過酸化水素がより好ましい。これらの酸化剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the oxidizing agent include ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, diammonium cerium nitrate, potassium hypochlorite, ozone, potassium periodate, peracetic acid, and the like. Among these oxidizing agents, at least one selected from potassium periodate, potassium hypochlorite, and hydrogen peroxide is preferred, and hydrogen peroxide is more preferred. These oxidizing agents may be used alone or in combination of two or more.
酸化剤を含有する場合、酸化剤の含有量は、第１化学機械研磨用組成物の全質量に対して、好ましくは０．００１～５質量％であり、より好ましくは０．００５～３質量％であり、特に好ましくは０．０１～１質量％である。 When containing an oxidizing agent, the content of the oxidizing agent is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, based on the total mass of the first chemical mechanical polishing composition. %, particularly preferably 0.01 to 1% by mass.
・界面活性剤
第１化学機械研磨用組成物は、界面活性剤を含有してもよい。界面活性剤には、第１化学機械研磨用組成物に適度な粘性を付与できる場合がある。
- Surfactant The first chemical mechanical polishing composition may contain a surfactant. The surfactant may be able to impart appropriate viscosity to the first chemical mechanical polishing composition.
界面活性剤としては、特に制限されず、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤等が挙げられる。アニオン性界面活性剤としては、例えば、脂肪酸石鹸、アルキルエーテルカルボン酸塩等のカルボン酸塩；アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、α－オレフィンスルホン酸塩等のスルホン酸塩；高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩等の硫酸塩；パーフルオロアルキル化合物等の含フッ素系界面活性剤等が挙げられる。カチオン性界面活性剤としては、例えば、脂肪族アミン塩及び脂肪族アンモニウム塩などが挙げられる。非イオン性界面活性剤としては、例えば、アセチレングリコール、アセチレングリコールエチレンオキサイド付加物、アセチレンアルコール等の三重結合を有する非イオン性界面活性剤；ポリエチレングリコール型界面活性剤等が挙げられる。これらの界面活性剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The surfactant is not particularly limited, and includes anionic surfactants, cationic surfactants, nonionic surfactants, and the like. Examples of anionic surfactants include fatty acid soaps, carboxylates such as alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates; higher alcohol sulfates; Examples include sulfates such as ester salts, alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates; fluorine-containing surfactants such as perfluoroalkyl compounds; Examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts. Examples of the nonionic surfactant include nonionic surfactants having a triple bond such as acetylene glycol, acetylene glycol ethylene oxide adduct, and acetylene alcohol; polyethylene glycol type surfactants, and the like. These surfactants may be used alone or in combination of two or more.
界面活性剤を含有する場合、界面活性剤の含有量は、第１化学機械研磨用組成物の全質量に対して、好ましくは０．００１～５質量％であり、より好ましくは０．００１～３質量％であり、特に好ましくは０．０１～１質量％である。 When containing a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.001 to 5% by mass, based on the total mass of the first chemical mechanical polishing composition. The amount is 3% by weight, particularly preferably 0.01 to 1% by weight.
・含窒素複素環化合物
第１化学機械研磨用組成物は、含窒素複素環化合物を含有してもよい。含窒素複素環化合物を含有することにより、配線金属の過剰なエッチングを抑制し、かつ、研磨後の表面荒れを防ぐことができる場合がある。
- Nitrogen-containing heterocyclic compound The first chemical mechanical polishing composition may contain a nitrogen-containing heterocyclic compound. By containing a nitrogen-containing heterocyclic compound, it may be possible to suppress excessive etching of the wiring metal and prevent surface roughening after polishing.
含窒素複素環化合物は、少なくとも１個の窒素原子を有する複素五員環及び複素六員環から選択される少なくとも１種の複素環を含む有機化合物である。前記複素環としては、ピロール構造、イミダゾール構造、トリアゾール構造等の複素五員環；ピリジン構造、ピリミジン構造、ピリダジン構造、ピラジン構造等の複素六員環が挙げられる。該複素環は縮合環を形成していてもよい。具体的には、インドール構造、イソインドール構造、ベンゾイミダゾール構造、ベンゾトリアゾール構造、キノリン構造、イソキノリン構造、キナゾリン構造、シンノリン構造、フタラジン構造、キノキサリン構造、アクリジン構造等が挙げられる。このような構造を有する複素環化合物のうち、ピリジン構造、キノリン構造、ベンゾイミダゾール構造、ベンゾトリアゾール構造を有する複素環化合物が好ましい。 The nitrogen-containing heterocyclic compound is an organic compound containing at least one type of heterocycle selected from five-membered heterocycles and six-membered heterocycles having at least one nitrogen atom. Examples of the heterocycle include five-membered heterocycles such as a pyrrole structure, imidazole structure, and triazole structure; six-membered heterocycles such as a pyridine structure, pyrimidine structure, pyridazine structure, and pyrazine structure. The heterocycle may form a fused ring. Specific examples include an indole structure, an isoindole structure, a benzimidazole structure, a benzotriazole structure, a quinoline structure, an isoquinoline structure, a quinazoline structure, a cinnoline structure, a phthalazine structure, a quinoxaline structure, and an acridine structure. Among the heterocyclic compounds having such a structure, those having a pyridine structure, a quinoline structure, a benzimidazole structure, or a benzotriazole structure are preferable.
含窒素複素環化合物の具体例としては、アジリジン、ピリジン、ピリミジン、ピロリジン、ピペリジン、ピラジン、トリアジン、ピロール、イミダゾール、インドール、キナルジン、キノリン、イソキノリン、ベンゾイソキノリン、プリン、プテリジン、トリアゾール、トリアゾリジン、ベンゾトリアゾール、カルボキシベンゾトリアゾール等が挙げられ、さらに、これらの骨格を有する誘導体が挙げられる。これらの含窒素複素環化合物は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Specific examples of nitrogen-containing heterocyclic compounds include aziridine, pyridine, pyrimidine, pyrrolidine, piperidine, pyrazine, triazine, pyrrole, imidazole, indole, quinaldine, quinoline, isoquinoline, benzisoquinoline, purine, pteridine, triazole, triazolidine, and benzotriazole. , carboxybenzotriazole, and derivatives having these skeletons. These nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
含窒素複素環化合物を含有する場合、含窒素複素環化合物の含有量は、第１化学機械研磨用組成物の全質量に対して、好ましくは０．０５～２質量％であり、より好ましくは０．１～１質量％である。 When containing a nitrogen-containing heterocyclic compound, the content of the nitrogen-containing heterocyclic compound is preferably 0.05 to 2% by mass, more preferably 0.05 to 2% by mass, based on the total mass of the first chemical mechanical polishing composition. It is 0.1 to 1% by mass.
・無機酸及びその塩
第１化学機械研磨用組成物は、無機酸及びその塩を含有してもよい。無機酸及びその塩を含有することにより、配線金属に対する研磨速度がさらに向上する場合がある。無機酸としては、例えば、塩酸、硝酸、硫酸、及びリン酸から選ばれる少なくとも１種が好ましい。無機酸の塩としては、上述の無機酸の塩であってもよく、化学機械研磨用組成物中で別途添加した塩基と上述の無機酸とが塩を形成してもよい。このような塩基としては、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等のアルカリ金属の水酸化物；テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリン等の有機アルカリ化合物、及びアンモニア等が挙げられる。
- Inorganic acid and its salt The first chemical mechanical polishing composition may contain an inorganic acid and its salt. By containing an inorganic acid and its salt, the polishing rate for wiring metal may be further improved. The inorganic acid is preferably at least one selected from, for example, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. The inorganic acid salt may be the above-mentioned inorganic acid salt, or the above-mentioned inorganic acid may form a salt with a base that is separately added in the chemical mechanical polishing composition. Examples of such bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; organic alkali compounds such as tetramethylammonium hydroxide (TMAH), choline, and ammonia. can be mentioned.
無機酸及びその塩を含有する場合、無機酸及びその塩の含有量は、第１化学機械研磨用組成物の全質量に対して、好ましくは３～８質量％であり、より好ましくは３～６質量％である。 When containing an inorganic acid and its salt, the content of the inorganic acid and its salt is preferably 3 to 8% by mass, more preferably 3 to 8% by mass, based on the total mass of the first chemical mechanical polishing composition. It is 6% by mass.
・水溶性高分子
第１化学機械研磨用組成物は、水溶性高分子を含有してもよい。水溶性高分子を含有することにより、樹脂膜や配線金属の表面に吸着して研磨摩擦を低減できる場合がある。このような水溶性高分子としては、ポリアクリル酸、ポリマレイン酸、ポリアクリルアミド、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンイミン、ポリビニルメチルエーテル、ポリアリルアミン、ヒドロキシエチルセルロース等が挙げられる。
- Water-soluble polymer The first chemical mechanical polishing composition may contain a water-soluble polymer. By containing a water-soluble polymer, it may be possible to reduce polishing friction by adsorbing to the surface of a resin film or wiring metal. Examples of such water-soluble polymers include polyacrylic acid, polymaleic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyvinyl methyl ether, polyallylamine, and hydroxyethyl cellulose.
水溶性高分子の重量平均分子量（Ｍｗ）は、好ましくは１，０００以上１，５００，０００以下であり、より好ましくは１０，０００以上５００，０００以下であり、特に好ましくは３０，０００以上１００，０００以下である。水溶性高分子の重量平均分子量が上記範囲内にあれば、水溶性高分子が樹脂膜や配線金属の表面に吸着しやすくなり、研磨摩擦がより低減する。その結果、被研磨面の研磨傷の発生をより効果的に低減することができる。なお、本明細書中における「重量平均分子量（Ｍｗ）」とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定されたポリエチレングリコール換算の重量
平均分子量のことを指す。
The weight average molecular weight (Mw) of the water-soluble polymer is preferably 1,000 or more and 1,500,000 or less, more preferably 10,000 or more and 500,000 or less, particularly preferably 30,000 or more and 100,000 or less. ,000 or less. If the weight average molecular weight of the water-soluble polymer is within the above range, the water-soluble polymer will be easily adsorbed to the surface of the resin film or wiring metal, and the polishing friction will be further reduced. As a result, the occurrence of polishing scratches on the surface to be polished can be more effectively reduced. In addition, the "weight average molecular weight (Mw)" in this specification refers to the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).
水溶性高分子の含有量は、第１化学機械研磨用組成物の全質量に対して、０．００１質量％以上が好ましく、０．００３質量％以上がより好ましく、０．０１質量％以上が特に好ましい。水溶性高分子の含有量が前記値以上であると、被研磨面の研磨傷の発生を低減することができる場合がある。水溶性高分子の含有量は、１質量％以下が好ましく、０．５質量％以下がより好ましく、０．１質量％以下が特に好ましい。水溶性高分子の含有量が前記値以下であると、被研磨面の研磨傷の発生を抑制しつつ、十分な研磨速度で研磨することができる場合がある。 The content of the water-soluble polymer is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and 0.01% by mass or more based on the total mass of the first chemical mechanical polishing composition. Particularly preferred. When the content of the water-soluble polymer is at least the above value, it may be possible to reduce the occurrence of polishing scratches on the surface to be polished. The content of the water-soluble polymer is preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less. When the content of the water-soluble polymer is below the above value, it may be possible to perform polishing at a sufficient polishing rate while suppressing the occurrence of polishing scratches on the surface to be polished.
なお、水溶性高分子の含有量は、水溶性高分子の重量平均分子量（Ｍｗ）にも依存するが、第１化学機械研磨用組成物の粘度が１０ｍＰａ・ｓ未満となるように調整することが好ましい。第１化学機械研磨用組成物の粘度が１０ｍＰａ・ｓ未満であると、樹脂膜や配線金属を高速で研磨しやすく、粘度が適正であるため研磨布上に安定して第１化学機械研磨用組成物を供給することができる。 The content of the water-soluble polymer depends on the weight average molecular weight (Mw) of the water-soluble polymer, but it should be adjusted so that the viscosity of the first chemical mechanical polishing composition is less than 10 mPa·s. is preferred. When the viscosity of the first chemical mechanical polishing composition is less than 10 mPa·s, it is easy to polish resin films and wiring metals at high speed, and since the viscosity is appropriate, it is stable on the polishing cloth and can be used for the first chemical mechanical polishing. A composition can be provided.
＜ｐＨ＞
第１化学機械研磨用組成物のｐＨは、１～６であることが好ましく、２～５であることがより好ましい。ｐＨが前記範囲であると、配線金属や樹脂膜を高速で研磨しやすくなり、被研磨面の平坦性を確保しやすく、さらに配線金属の腐食を抑制することができる。
<pH>
The pH of the first chemical mechanical polishing composition is preferably 1 to 6, more preferably 2 to 5. When the pH is within the above range, it becomes easy to polish the wiring metal and the resin film at high speed, it is easy to ensure the flatness of the surface to be polished, and corrosion of the wiring metal can be suppressed.
なお、第１化学機械研磨用組成物のｐＨは、例えば、前記（Ｂ）有機酸、前記無機酸及びその塩などの酸や、水酸化カリウム、エチレンジアミン、ＴＭＡＨ（テトラメチルアンモニウムハイドロオキサイド）、アンモニア等の塩基の添加量を適宜増減することにより調整することができ、これらの１種以上を用いることができる。 Note that the pH of the first chemical mechanical polishing composition is determined by, for example, acids such as the organic acid (B), the inorganic acid, and their salts, potassium hydroxide, ethylenediamine, TMAH (tetramethylammonium hydroxide), and ammonia. It can be adjusted by appropriately increasing or decreasing the amount of bases added, and one or more of these bases can be used.
本発明において、ｐＨは、水素イオン指数のことを指し、その値は、２５℃、１気圧の条件下で市販のｐＨメーター（例えば、株式会社堀場製作所製、卓上型ｐＨメーター）を用いて測定することができる。 In the present invention, pH refers to the hydrogen ion index, and its value is measured using a commercially available pH meter (for example, a desktop pH meter manufactured by Horiba, Ltd.) at 25°C and 1 atm. can do.
＜第１化学機械研磨用組成物の調製方法＞
第１化学機械研磨用組成物は、水等の液状媒体に上述した各成分を溶解または分散させることにより調製することができる。溶解または分散させる方法は、特に制限されず、均一に溶解または分散できればどのような方法を適用してもよい。また、上述した各成分の混合順序や混合方法についても特に制限されない。
<Method for preparing first chemical mechanical polishing composition>
The first chemical mechanical polishing composition can be prepared by dissolving or dispersing the above-mentioned components in a liquid medium such as water. The method for dissolving or dispersing is not particularly limited, and any method may be used as long as it can be uniformly dissolved or dispersed. Furthermore, there are no particular restrictions on the mixing order or mixing method of each of the above-mentioned components.
また、第１化学機械研磨用組成物は、使用時に水等の液状媒体で希釈して使用するための原液であってもよい。 Further, the first chemical mechanical polishing composition may be a stock solution that is diluted with a liquid medium such as water before use.
１．１．２．化学機械研磨装置
第１研磨工程には、例えば図５に示すような化学機械研磨装置３００を用いることができる。図５は、化学機械研磨装置３００を模式的に示した斜視図である。第１研磨工程は、スラリー供給ノズル４２からスラリー（化学機械研磨用組成物）４４を供給し、かつ、研磨布４６が貼付されたターンテーブル４８を回転させながら、回路基板５０を保持したキャリアーヘッド５２を当接させることにより行う。なお、図５には、水供給ノズル５４及びドレッサー５６も併せて示してある。
1.1.2. Chemical Mechanical Polishing Apparatus For the first polishing process, a chemical
キャリアーヘッド５２の研磨荷重は、０．７～７０ｐｓｉの範囲内で選択することができ、好ましくは１．５～３５ｐｓｉである。また、ターンテーブル４８及びキャリアーヘッド５２の回転数は１０～４００ｒｐｍの範囲内で適宜選択することができ、好ましくは
３０～１５０ｒｐｍである。スラリー供給ノズル４２から供給されるスラリー（化学機械研磨用組成物）４４の流量は、１０～１，０００ｍＬ／分の範囲内で選択することができ、好ましくは５０～４００ｍＬ／分である。
The polishing load of the
市販の研磨装置としては、例えば、荏原製作所社製、型式「ＥＰＯ－１１２」、「ＥＰＯ－２２２」；ラップマスターＳＦＴ社製、型式「ＬＧＰ－５１０」、「ＬＧＰ－５５２」；アプライドマテリアル社製、型式「Ｍｉｒｒａ」、「Ｒｅｆｌｅｘｉｏｎ」；Ｇ＆Ｐ
ＴＥＣＨＮＯＬＯＧＹ社製、型式「ＰＯＬＩ－４００Ｌ」；ＡＭＡＴ社製、型式「Ｒｅｆｌｅｘｉｏｎ ＬＫ」等が挙げられる。
Commercially available polishing devices include, for example, manufactured by Ebara Corporation, models "EPO-112" and "EPO-222"; manufactured by Lapmaster SFT, models "LGP-510" and "LGP-552"; manufactured by Applied Materials, Inc. , model "Mirra", "Reflexion";G&P
Examples include TECHNOLOGY Co., model "POLI-400L"; AMAT Co., model "Reflexion LK".
１．２．第２研磨工程
図２は、図１に示す被処理体の第１研磨工程終了後の状態を模式的に示した断面図である。図３は、図２に示す被処理体の第２研磨工程終了後の状態を模式的に示した断面図である。第２研磨工程は、図２に示すような前記第１研磨工程後の被研磨面を、さらに（Ａ２）シリカ粒子を含有する第２化学機械研磨用組成物を使用して研磨する工程である。図２に示すように、第１研磨工程後の被研磨面は、配線金属１０上の一部もしくは全部に樹脂膜１２が残存していることがあるため、該樹脂膜１２を除去する必要がある。第２化学機械研磨用組成物に含有される（Ａ２）シリカ粒子は、（Ａ１）アルミナ含有粒子よりも硬度が低く、銅や銅合金などの柔らかな配線金属を研磨する用途に適している。そのため、第２化学機械研磨用組成物は、配線金属や樹脂膜に対する研磨速度が第１化学機械研磨用組成物に比べて低いものの、配線金属／樹脂膜が共存する被研磨面を精密かつスクラッチ発生を低減しながら研磨することができる。したがって、第２研磨工程を経ることにより、図３に示すような高平坦性を有し、かつ、配線金属のスクラッチが低減された回路基板２００が得られる。
1.2. Second Polishing Step FIG. 2 is a cross-sectional view schematically showing the state of the object shown in FIG. 1 after the first polishing step. FIG. 3 is a cross-sectional view schematically showing the state of the object to be processed shown in FIG. 2 after the second polishing step. The second polishing step is a step of polishing the surface to be polished after the first polishing step as shown in FIG. 2 using a second chemical mechanical polishing composition containing (A2) silica particles. . As shown in FIG. 2, the
１．２．１．第２化学機械研磨用組成物
＜（Ａ２）シリカ粒子＞
第２化学機械研磨用組成物は、（Ａ２）シリカ粒子を含有する。（Ａ２）シリカ粒子としては、例えば、気相中で塩化ケイ素、塩化アルミニウム、塩化チタン等を酸素および水素と反応させるヒュームド法により合成されたシリカ粒子；金属アルコキシドから加水分解縮合して合成するゾルゲル法により合成されたシリカ粒子；精製により不純物を除去した無機コロイド法等により合成されたコロイダルシリカ粒子が挙げられる。これらの中でも、分散安定性に優れ、また粒子径の制御が容易で、粗大粒子によるスクラッチの発生を抑制しやすいため、コロイダルシリカ粒子が好ましい。
1.2.1. Second chemical mechanical polishing composition <(A2) silica particles>
The second chemical mechanical polishing composition contains (A2) silica particles. (A2) Silica particles include, for example, silica particles synthesized by a fumed method in which silicon chloride, aluminum chloride, titanium chloride, etc. are reacted with oxygen and hydrogen in a gas phase; sol gel synthesized by hydrolytic condensation from metal alkoxides; Examples include silica particles synthesized by a method; and colloidal silica particles synthesized by an inorganic colloid method in which impurities are removed by purification. Among these, colloidal silica particles are preferred because they have excellent dispersion stability, are easy to control the particle size, and are easy to suppress the occurrence of scratches due to coarse particles.
（Ａ２）シリカ粒子の形状は、特開２０１２－１０４８００号公報に記載の母粒子の表面に疣状突起を有する略球状であることが好ましい。このような形状を有する（Ａ２）シリカ粒子であれば、配線金属や樹脂膜を適切な研磨速度で研磨できるだけでなく、被研磨面におけるスクラッチ等の発生も低減できる。 (A2) The shape of the silica particles is preferably approximately spherical with wart-like protrusions on the surface of the mother particle described in JP-A-2012-104800. Silica particles (A2) having such a shape can not only polish wiring metals and resin films at an appropriate polishing rate, but also reduce the occurrence of scratches and the like on the surface to be polished.
（Ａ２）シリカ粒子の平均一次粒子径は、好ましくは０．０１～０．１μｍであり、より好ましくは０．０１～０．０８μｍであり、特に好ましくは０．０２～０．０５μｍである。上記範囲の平均一次粒子径を有する（Ａ２）シリカ粒子であれば、配線金属や樹脂膜に対する適切な研磨速度が得られると共に、粒子の沈降・分離を生ずることのない安定性に優れた化学機械研磨用組成物が得られるため、良好な研磨特性が得られる。なお、（Ａ２）シリカ粒子の平均一次粒子径は、原料となるシリカ粒子分散体の一部を乾燥させて得られた試料について、透過型電子顕微鏡を用いて凝集した個々の粒子を観察して一次粒子径を求め、それらを平均化して求めることができる。 (A2) The average primary particle diameter of the silica particles is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.08 μm, particularly preferably 0.02 to 0.05 μm. (A2) silica particles having an average primary particle diameter within the above range can provide a suitable polishing rate for wiring metals and resin films, and can also be used as a chemical machine with excellent stability without causing sedimentation or separation of particles. Since a polishing composition is obtained, good polishing properties can be obtained. (A2) The average primary particle diameter of the silica particles is determined by observing individual aggregated particles using a transmission electron microscope on a sample obtained by drying a part of the silica particle dispersion that is the raw material. It can be determined by determining the primary particle diameter and averaging them.
（Ａ２）シリカ粒子の平均二次粒子径は、好ましくは０．０２～０．３μｍであり、よ
り好ましくは０．０２～０．２μｍであり、特に好ましくは０．０３～０．１μｍである。上記範囲の平均二次粒子径を有する（Ａ２）シリカ粒子であれば、配線金属や樹脂膜に対する適切な研磨速度が得られると共に、粒子の沈降・分離を生ずることのない安定性に優れた化学機械研磨用組成物が得られるため、良好な研磨特性が得られる。ここで、「二次粒子」とは、一次粒子が凝集した状態のことをいう。シリカ粒子は、化学機械研磨用組成物中では、通常二次粒子の状態で存在している。なお、シリカ粒子の平均二次粒子径は、動的光散乱式粒子径測定装置（株式会社堀場製作所製、型式「ＬＢ５５０」）を用いて測定された算術平均径を平均二次粒子径として求めることができる。
(A2) The average secondary particle diameter of the silica particles is preferably 0.02 to 0.3 μm, more preferably 0.02 to 0.2 μm, particularly preferably 0.03 to 0.1 μm. . Silica particles (A2) having an average secondary particle diameter within the above range can provide an appropriate polishing rate for wiring metals and resin films, and are chemically stable with no sedimentation or separation of particles. Since a composition for mechanical polishing is obtained, good polishing properties can be obtained. Here, the term "secondary particles" refers to a state in which primary particles are aggregated. Silica particles usually exist in the form of secondary particles in chemical mechanical polishing compositions. The average secondary particle diameter of the silica particles is determined by the arithmetic mean diameter measured using a dynamic light scattering particle diameter measuring device (manufactured by Horiba, Ltd., model "LB550") as the average secondary particle diameter. be able to.
（Ａ２）シリカ粒子の含有量は、第２化学機械研磨用組成物の全質量に対して、０．５質量％以上が好ましく、１．０質量％以上がより好ましく、３．０質量％以上が特に好ましい。（Ａ２）シリカ粒子の含有量が前記値以上であれば、配線金属及び樹脂膜を研磨することができる。（Ａ２）シリカ粒子の含有量は、１５．０質量％以下が好ましく、１２．０質量％以下がより好ましく、９．０質量％以下が特に好ましい。（Ａ２）シリカ粒子の含有量が前記値以下であれば、被研磨面の研磨傷の発生を低減することができる。 (A2) The content of silica particles is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and 3.0% by mass or more based on the total mass of the second chemical mechanical polishing composition. is particularly preferred. (A2) If the content of silica particles is at least the above value, the wiring metal and the resin film can be polished. (A2) The content of silica particles is preferably 15.0% by mass or less, more preferably 12.0% by mass or less, particularly preferably 9.0% by mass or less. (A2) If the content of silica particles is below the above value, the occurrence of polishing scratches on the surface to be polished can be reduced.
＜その他の添加剤＞
第２化学機械研磨用組成物は、主要な液状媒体である水の他、必要に応じて、（Ｂ）有機酸、酸化剤、界面活性剤、含窒素複素環化合物、無機酸及びその塩、水溶性高分子等を含有してもよい。これらの添加剤については、上述の第１化学機械研磨用組成物のところで説明した各化合物を例示することができ、また含有量については、上述の第１化学機械研磨用組成物のところで説明した含有量と同量とすることができる。
<Other additives>
The second chemical mechanical polishing composition contains, in addition to water as the main liquid medium, (B) an organic acid, an oxidizing agent, a surfactant, a nitrogen-containing heterocyclic compound, an inorganic acid and its salt, It may also contain water-soluble polymers and the like. Examples of these additives include the compounds explained in the above-mentioned first chemical mechanical polishing composition, and the contents are as explained in the above-mentioned first chemical mechanical polishing composition. It can be made the same amount as the content.
＜ｐＨ＞
第２化学機械研磨用組成物のｐＨは、１～６であることが好ましく、２～５であることがより好ましい。ｐＨが前記範囲であると、配線金属／樹脂膜が共存する被研磨面の平坦性を確保しやすく、さらに配線金属の腐食を抑制することができる。
<pH>
The pH of the second chemical mechanical polishing composition is preferably 1 to 6, more preferably 2 to 5. When the pH is within the above range, it is easy to ensure the flatness of the surface to be polished where the wiring metal/resin film coexists, and furthermore, corrosion of the wiring metal can be suppressed.
なお、第２化学機械研磨用組成物のｐＨは、例えば、前記（Ｂ）有機酸、前記無機酸及びその塩などの酸や、水酸化カリウム、エチレンジアミン、ＴＭＡＨ（テトラメチルアンモニウムハイドロオキサイド）、アンモニア等の塩基の添加量を適宜増減することにより調整することができ、これらの１種以上を用いることができる。 Note that the pH of the second chemical mechanical polishing composition is determined by, for example, acids such as the organic acids (B), the inorganic acids, and their salts, potassium hydroxide, ethylenediamine, TMAH (tetramethylammonium hydroxide), and ammonia. It can be adjusted by appropriately increasing or decreasing the amount of bases added, and one or more of these bases can be used.
＜第２化学機械研磨用組成物の調製方法＞
第２化学機械研磨用組成物は、水等の液状媒体に上述した各成分を溶解または分散させることにより調製することができる。溶解または分散させる方法は、特に制限されず、均一に溶解または分散できればどのような方法を適用してもよい。また、上述した各成分の混合順序や混合方法についても特に制限されない。
<Method for preparing second chemical mechanical polishing composition>
The second chemical mechanical polishing composition can be prepared by dissolving or dispersing the above-mentioned components in a liquid medium such as water. The method for dissolving or dispersing is not particularly limited, and any method may be used as long as it can be uniformly dissolved or dispersed. Furthermore, there are no particular restrictions on the mixing order or mixing method of each of the above-mentioned components.
また、第２化学機械研磨用組成物は、使用時に水等の液状媒体で希釈して使用するための原液であってもよい。 Further, the second chemical mechanical polishing composition may be a stock solution that is diluted with a liquid medium such as water before use.
１．２．２．化学機械研磨装置
第２研磨工程においても、例えば図５に示すような化学機械研磨装置３００を用いることができる。化学機械研磨装置の構成、操作、使用条件、及び市販製品等については、第１研磨工程と同様である。
1.2.2. Chemical Mechanical Polishing Apparatus Also in the second polishing process, a chemical
２．実施例
以下、本発明を実施例により説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、本実施例における「部」および「％」は、特に断らない限り質量
基準である。
2. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, "part" and "%" in this example are based on mass unless otherwise specified.
２．１．アルミナ含有粒子の物性測定
＜アルミナ含有粒子のＸ線回折強度測定＞
アルミナ含有粒子の粉末Ｘ線回折パターンにおける回折強度が最大となるピーク部分の半値幅は、以下の条件で測定した。
・装置：全自動水平型多目的Ｘ線回折装置ＳｍａｒｔＬａｂ（リガク社製）
・Ｘ線源：ＣｕＫα ３ｋｗ（水冷）
・測定方法：ガラス試料板を用いた粉末法
・スリット：パラレルビーム（ＰＢ）分解能（中レベル）
・測定範囲：１５ｄｅｇ－１２０ｄｅｇ
・ステップ：０．０５ｄｅｇ
・スキャンスピード：０．５ｄｅｇ／ｍｉｎ（連続）
2.1. Measurement of physical properties of alumina-containing particles <Measurement of X-ray diffraction intensity of alumina-containing particles>
The half-value width of the peak portion where the diffraction intensity is maximum in the powder X-ray diffraction pattern of the alumina-containing particles was measured under the following conditions.
・Device: Fully automatic horizontal multipurpose X-ray diffraction device SmartLab (manufactured by Rigaku Corporation)
・X-ray source: CuKα 3kw (water cooling)
・Measurement method: Powder method using a glass sample plate ・Slit: Parallel beam (PB) resolution (medium level)
・Measurement range: 15deg-120deg
・Step: 0.05deg
・Scan speed: 0.5deg/min (continuous)
＜アルミナ含有粒子の平均一次粒子径＞
アルミナ含有粒子を乾燥させて得られた試料について、流動式比表面積自動測定装置（株式会社島津製作所製、「ｍｉｃｒｏｍｅｔｒｉｃｓＦｌｏｗＳｏｒｂＩＩ２３００」）を用いてＢＥＴ法による比表面積を測定し、その測定値から算出して平均一次粒子径を求めた。
<Average primary particle diameter of alumina-containing particles>
The specific surface area of the sample obtained by drying the alumina-containing particles was measured by the BET method using a flow type automatic specific surface area measurement device (manufactured by Shimadzu Corporation, "micrometrics FlowSorb II 2300"), and the specific surface area was calculated from the measured value. The average primary particle diameter was determined.
＜アルミナ含有粒子のＳｉ含有量＞
ＪＩＳ Ｒ１６４９：２００２に記載されている測定法に準じて測定した。具体的には、試料となるアルミナ含有粒子に硫酸を加えて加圧分解容器中で加熱して溶解し試料溶液を調製し、その溶液をＩＣＰ発光分光分析装置（島津製作所社製、型式「ＩＣＰＥ－９８００」）のアルゴンプラズマ中に噴霧し、Ｓｉの発光強度を測定することにより、アルミナ含有粒子中のＳｉ含有量を求めた。
<Si content of alumina-containing particles>
The measurement was performed according to the measurement method described in JIS R1649:2002. Specifically, a sample solution is prepared by adding sulfuric acid to alumina-containing particles that serve as a sample and dissolving them by heating in a pressure decomposition container. The Si content in the alumina-containing particles was determined by spraying the alumina-containing particles into an argon plasma of -9800'' and measuring the emission intensity of Si.
＜アルミナ含有粒子の真比重＞
ＪＩＳ ９３０１－２－１：１９９９に記載されている「ピクノメーター法による真密度」測定法に準じて測定した。
<True specific gravity of alumina-containing particles>
It was measured according to the "true density by pycnometer method" measurement method described in JIS 9301-2-1:1999.
＜アルミナ含有粒子のＲｍａｘ／Ｒｍｉｎ測定＞
アルミナ含有粒子の一部を、透過型電子顕微鏡を用いて５０個の粒子を観察し、各々のアルミナ含有粒子の長径（Ｒｍａｘ）及び短径（Ｒｍｉｎ）を測定し、各々のアルミナ含有粒子の比率（Ｒｍａｘ／Ｒｍｉｎ）を求め、それを平均化したものを表１及び表２に併せて示した。
<Rmax/Rmin measurement of alumina-containing particles>
Some of the alumina-containing particles were observed using a transmission electron microscope, and the major axis (Rmax) and minor axis (Rmin) of each alumina-containing particle were measured, and the ratio of each alumina-containing particle was determined. (Rmax/Rmin) was calculated, and the averaged values are shown in Tables 1 and 2.
２．２．第１化学機械研磨用組成物の調製
表１又は表２に記載のアルミナ含有粒子及びイオン交換水を容量１リットルのポリエチレン製の瓶に投入し、これに表１又は表２に記載の有機酸を添加して、組成物のｐＨが表１又は表２に記載の値となるように調整するとともに、各成分の合計量が１００質量部となるようにイオン交換水で調整した。その後、孔径５μｍのフィルターで濾過することにより、実施例１～１４及び比較例１～６、１０で用いる化学機械研磨用組成物を得た。
2.2. Preparation of first chemical mechanical polishing composition Alumina-containing particles listed in Table 1 or Table 2 and ion-exchanged water are placed in a polyethylene bottle with a capacity of 1 liter, and an organic acid listed in Table 1 or Table 2 is poured into a polyethylene bottle with a capacity of 1 liter. was added to adjust the pH of the composition to the values listed in Table 1 or Table 2, and the total amount of each component was adjusted with ion-exchanged water to be 100 parts by mass. Thereafter, the chemical mechanical polishing compositions used in Examples 1 to 14 and Comparative Examples 1 to 6 and 10 were obtained by filtering through a filter with a pore size of 5 μm.
２．３．第２化学機械研磨用組成物の調製
特開２００９－１６１３７１号公報の００６７段落に記載の実施例１に準じて（Ａ２－１）シリカ粒子分散体を、００６８段落に記載の実施例２に準じて（Ａ２－２）シリカ粒子分散体を、００６９段落に記載の実施例３に準じて（Ａ２－３）シリカ粒子分散体をそれぞれ作製した。その後、ロータリーエバポレータを用い、得られた前記分散体の温度を８０℃に維持しながらイオン交換水を添加しつつアルコールを除去する操作を数回繰り返
した。その後、表２に記載の有機酸を添加して、分散体のｐＨを表２に記載の値となるように調整するとともに、各成分の合計量が１００質量部となるようにイオン交換水で調整し、実施例１０～１４及び比較例７～１０で用いる化学機械研磨用組成物を得た。
2.3. Preparation of second chemical mechanical polishing composition According to Example 1 described in paragraph 0067 of JP-A-2009-161371, (A2-1) silica particle dispersion was added according to Example 2 described in paragraph 0068. According to Example 3 described in paragraph 0069, (A2-3) a silica particle dispersion was prepared. Thereafter, using a rotary evaporator, the operation of removing alcohol while maintaining the temperature of the resulting dispersion at 80° C. while adding ion-exchanged water was repeated several times. Thereafter, the organic acid listed in Table 2 was added to adjust the pH of the dispersion to the value listed in Table 2, and ion-exchanged water was added so that the total amount of each component was 100 parts by mass. The chemical mechanical polishing compositions used in Examples 10 to 14 and Comparative Examples 7 to 10 were obtained.
２．４．評価方法
２．４．１．研磨速度評価
＜評価用基板の作製＞
８インチのシリコンウエハーにＷＰＲ－１２０１（ＪＳＲ株式会社製、ネガ型感光性絶縁膜）をスピンコートし、その後、ホットプレートを用いて加熱・硬化し、シリコンウエハー上に厚さ２０μｍの均一な樹脂膜を作製した。このようにして得られた基板を研磨速度評価に使用した。
2.4. Evaluation method 2.4.1. Polishing rate evaluation <Preparation of evaluation substrate>
WPR-1201 (manufactured by JSR Corporation, negative photosensitive insulating film) is spin-coated on an 8-inch silicon wafer, and then heated and cured using a hot plate to form a uniform resin with a thickness of 20 μm on the silicon wafer. A membrane was prepared. The substrate thus obtained was used for polishing rate evaluation.
＜研磨速度の評価方法＞
（実施例１～９及び比較例１～３）
上記で調製した化学機械研磨用組成物を用いて、上記で得られた評価用基板を４ｃｍ×４ｃｍに切断した試験片を被研磨体として、下記の研磨条件で４分間の化学機械研磨試験を行った。
（実施例１０～１４及び比較例４～１０）
まず、第１研磨工程では、上記で調製した化学機械研磨用組成物を用いて、上記で得られた評価用基板を４ｃｍ×４ｃｍに切断した試験片を被研磨体として、下記の研磨条件で４分間の化学機械研磨試験を行った。次いで、第２研磨工程では、上記研磨後の被研磨面を、上記で調製した化学機械研磨用組成物を用いて同様の化学機械研磨試験をさらに実施した。
（研磨条件）
・研磨装置：Ｇ＆Ｐ ＴＥＣＨＮＯＬＯＧＹ社製、型式「ＰＯＬＩ－４００Ｌ」
・研磨パッド：ニッタ・ハース製、「ＩＣ１０００」
・化学機械研磨用組成物供給速度：２００ｍＬ／分
・定盤回転数：１００ｒｐｍ
・ヘッド回転数：９０ｒｐｍ
・研磨ヘッド押し付け圧：１４０ｈＰａ
<Evaluation method of polishing rate>
(Examples 1 to 9 and Comparative Examples 1 to 3)
Using the chemical mechanical polishing composition prepared above, a chemical mechanical polishing test was conducted for 4 minutes under the following polishing conditions using a test piece obtained by cutting the evaluation substrate obtained above into 4 cm x 4 cm as the object to be polished. went.
(Examples 10 to 14 and Comparative Examples 4 to 10)
First, in the first polishing step, the chemical-mechanical polishing composition prepared above was used, and a test piece obtained by cutting the evaluation substrate obtained above into 4 cm x 4 cm was used as the object to be polished, under the following polishing conditions. A 4 minute chemical mechanical polishing test was conducted. Next, in the second polishing step, the polished surface was further subjected to a similar chemical mechanical polishing test using the chemical mechanical polishing composition prepared above.
(polishing conditions)
- Polishing device: Manufactured by G&P TECHNOLOGY, model "POLI-400L"
・Polishing pad: “IC1000” manufactured by Nitta Haas
・Chemical mechanical polishing composition supply rate: 200 mL/min ・Surface plate rotation speed: 100 rpm
・Head rotation speed: 90rpm
・Pressing pressure of polishing head: 140hPa
研磨速度は、下記式により計算して求めた。なお、各膜の厚さは、マイクロメータ（ミツトヨ社製、型式「ＭＤＨ－２５Ｈ」）を用いて測定した。
・研磨速度（μｍ／ｍｉｎ）＝［（研磨前の各膜の厚さ（μｍ））－（研磨後の各膜の厚さ（μｍ））］／研磨時間（ｍｉｎ）
The polishing rate was calculated using the following formula. The thickness of each film was measured using a micrometer (manufactured by Mitutoyo, model "MDH-25H").
- Polishing speed (μm/min) = [(Thickness of each film before polishing (μm)) - (Thickness of each film after polishing (μm))] / Polishing time (min)
実施例１～９及び比較例１～３における研磨速度評価並びに実施例１０～１４及び比較例４～１０の第１研磨工程における研磨速度の評価基準は下記の通りである。各膜の研磨速度及び評価結果を表１及び表２に併せて示す。
（評価基準）
・研磨速度が２μｍ／ｍｉｎ以上である場合、樹脂膜に対する研磨速度が十分に大きく、実際のプリント基板研磨においても高速処理が可能であり、実用的であるため良好と判断し「○」と表記した。
・研磨速度が２μｍ／ｍｉｎ未満である場合、樹脂膜に対する研磨速度が小さく、実際のプリント基板研磨において実用困難であるため不良と判断し「×」と表記した。
The evaluation criteria for the polishing rate in Examples 1 to 9 and Comparative Examples 1 to 3 and the polishing rate in the first polishing step in Examples 10 to 14 and Comparative Examples 4 to 10 are as follows. The polishing rate and evaluation results of each film are also shown in Tables 1 and 2.
(Evaluation criteria)
・If the polishing rate is 2 μm/min or more, the polishing rate for the resin film is sufficiently high and high-speed processing is possible even in actual printed circuit board polishing, so it is judged to be good and is marked as "○". did.
- When the polishing rate is less than 2 μm/min, the polishing rate for the resin film is low and it is difficult to put it into practical use in actual printed circuit board polishing, so it is judged to be defective and marked as "x".
２．４．２．平坦性評価
＜評価用基板の作製＞
８インチのシリコンウエハーにＷＰＲ－１２０１（ＪＳＲ株式会社製、ネガ型感光性絶縁膜）をスピンコートし、その後、ホットプレートを用いて加熱・硬化し、厚さ２０μｍ
の均一な樹脂硬化膜を作製した。次いで、アライナー（ＳＵＳＳ ＭｉｃｒｏＴｅｃ社製、型式「ＭＡ－２００」）を使用し、高圧水銀灯から照射される紫外線を、波長３６５ｎｍにおける露光量が５００ｍＪ／ｃｍ２となるように露光した。その後、ホットプレートを用いて１１０℃で３分間加熱（ＰＥＢ）し、２．３８質量％濃度のテトラメチルアンモニウムハイドロキサイド水溶液を用いて２３℃で１２０秒間浸漬し、現像した。
その後、絶縁樹脂硬化膜上に無電解めっきにより銅シード層を形成し、その後電解メッキ法により３０μｍの銅メッキ層を形成し、溝パターン内に銅を埋め込んだ基板を作製した。次に、特許第５３２１７９６号公報または特許第５４５９４６７号公報に記載の化学機械研磨用組成物を用いて、溝パターン以外の銅を除去し、１００μｍ幅の導電層ラインを露出させた。その後、再度、ＷＰＲ－１２０１（ＪＳＲ株式会社製、感光性絶縁膜）をスピンコートし、ホットプレートを用いて加熱・硬化し、厚さ２０μｍの樹脂硬化膜を形成した。このようにして得られた基板を平坦性評価に使用した。なお、本方法により作製した基板は、回路基板を模した平坦性評価用基板である。
2.4.2. Flatness evaluation <Preparation of evaluation substrate>
WPR-1201 (manufactured by JSR Corporation, negative photosensitive insulating film) was spin-coated on an 8-inch silicon wafer, and then heated and cured using a hot plate to a thickness of 20 μm.
A uniform cured resin film was prepared. Next, using an aligner (manufactured by SUSS MicroTec, model "MA-200"), the sample was exposed to ultraviolet rays emitted from a high-pressure mercury lamp so that the exposure amount at a wavelength of 365 nm was 500 mJ/cm 2 . Thereafter, it was heated (PEB) at 110° C. for 3 minutes using a hot plate, and developed by immersing it in a 2.38% by mass aqueous tetramethylammonium hydroxide solution at 23° C. for 120 seconds.
Thereafter, a copper seed layer was formed on the cured insulating resin film by electroless plating, and then a 30 μm copper plating layer was formed by electrolytic plating to produce a substrate in which copper was embedded in the groove pattern. Next, using a chemical mechanical polishing composition described in Japanese Patent No. 5321796 or Japanese Patent No. 5459467, copper other than the groove pattern was removed to expose a 100 μm wide conductive layer line. Thereafter, WPR-1201 (manufactured by JSR Corporation, photosensitive insulating film) was spin-coated again, and heated and cured using a hot plate to form a cured resin film with a thickness of 20 μm. The substrate thus obtained was used for flatness evaluation. Note that the substrate produced by this method is a flatness evaluation substrate imitating a circuit board.
＜平坦性の評価方法＞
上記で調製した化学機械研磨用組成物を用いて、上記で得られた平坦性評価用基板を４ｃｍ×４ｃｍに切断した試験片を被研磨体として、下記の研磨条件で１０分間の化学機械研磨試験を行い、樹脂面に対する銅の飛び出し高さ（銅凸高さ）を測定した。なお、銅凸高さの評価は、レーザー顕微鏡（オリンパス社製、型式「ＯＬＳ４０００」）を使用して測定した。評価基準は以下の通りである。銅の飛び出し高さ（μｍ）及び評価結果を表１及び表２に併せて示す。
（研磨条件）
・研磨装置：Ｇ＆Ｐ ＴＥＣＨＮＯＬＯＧＹ社製、型式「ＰＯＬＩ－４００Ｌ」
・研磨パッド：ニッタ・ハース製、「ＩＣ１０００」
・化学機械研磨用組成物供給速度：２００ｍＬ／分
・定盤回転数：１００ｒｐｍ
・ヘッド回転数：９０ｒｐｍ
・研磨ヘッド押し付け圧：１４０ｈＰａ
（評価基準）
・銅凸高さが０．３μｍ未満である場合、平坦性が十分に確保されており、非常に良好と判断し「◎」と表記した。
・銅凸高さが０．３μｍ以上０．６μｍ未満である場合、平坦性が確保されており、良好と判断し「○」と表記した。
・銅凸高さが０．６μｍ以上である場合又は評価ができなかった場合、平坦性が確保できず、実用困難であるため不良と判断し「×」と表記した。
<Flatness evaluation method>
Using the chemical mechanical polishing composition prepared above, a test piece obtained by cutting the flatness evaluation substrate obtained above into 4 cm x 4 cm was used as the object to be polished, and chemical mechanical polishing was performed for 10 minutes under the following polishing conditions. A test was conducted and the height of copper protrusion from the resin surface (copper protrusion height) was measured. In addition, the evaluation of the copper convex height was measured using a laser microscope (manufactured by Olympus Corporation, model "OLS4000"). The evaluation criteria are as follows. The protrusion height (μm) of copper and the evaluation results are also shown in Tables 1 and 2.
(polishing conditions)
- Polishing device: Manufactured by G&P TECHNOLOGY, model "POLI-400L"
・Polishing pad: “IC1000” manufactured by Nitta Haas
・Chemical mechanical polishing composition supply rate: 200 mL/min ・Surface plate rotation speed: 100 rpm
・Head rotation speed: 90rpm
・Pressing pressure of polishing head: 140hPa
(Evaluation criteria)
- When the copper protrusion height is less than 0.3 μm, the flatness is sufficiently ensured, and it is judged to be very good, and it is marked as “◎”.
- When the height of the copper convexity is 0.3 μm or more and less than 0.6 μm, flatness is ensured, and it is judged as good and is marked as “○”.
- If the height of the copper convexity is 0.6 μm or more, or if it could not be evaluated, flatness could not be ensured and it was difficult to put it into practical use, so it was judged to be defective and was marked as "x".
２．４．３．表面粗さの評価
（実施例１０～１４及び比較例４～１０）
上記の研磨速度評価で得られた第２研磨工程終了後の被研磨面について、樹脂面に対する表面粗さ（算術平均高さＳａ）を測定した。評価基準は以下の通りである。その結果を表２に併せて示す。
（評価基準）
・算術平均高さが２０ｎｍ未満である場合、平坦性が良好であると判断し「○」と表記した。
・算術平均高さが２０ｎｍ以上である場合、平坦性が不良であると判断し「×」と表記した。
2.4.3. Evaluation of surface roughness (Examples 10 to 14 and Comparative Examples 4 to 10)
The surface roughness (arithmetic mean height Sa) with respect to the resin surface was measured for the surface to be polished after the second polishing step obtained in the above polishing rate evaluation. The evaluation criteria are as follows. The results are also shown in Table 2.
(Evaluation criteria)
- When the arithmetic mean height was less than 20 nm, it was determined that the flatness was good and was marked as "○".
- When the arithmetic mean height was 20 nm or more, it was determined that the flatness was poor and was marked as "×".
２．４．４．スクラッチの評価
（実施例１０～１４及び比較例４～１０）
上記の平坦性評価で得られた基板を用いて、下記の研磨条件で４分間の第２研磨工程終
了後の被研磨面について、銅面に対するスクラッチの有無を、光学顕微鏡を用いて暗視野にて観察した。評価基準は以下の通りである。その結果を表２に併せて示す。
（研磨条件）
・研磨装置：Ｇ＆Ｐ ＴＥＣＨＮＯＬＯＧＹ社製、型式「ＰＯＬＩ－４００Ｌ」
・研磨パッド：ニッタ・ハース製、「ＩＣ１０００」
・化学機械研磨用組成物供給速度：２００ｍＬ／分
・定盤回転数：１００ｒｐｍ
・ヘッド回転数：９０ｒｐｍ
・研磨ヘッド押し付け圧：１４０ｈＰａ
（評価基準）
・スクラッチがない場合、表面状態が良好であると判断し「○」と表記した。
・スクラッチがある場合、表面状態が不良であると判断し「×」と表記した。
2.4.4. Evaluation of scratches (Examples 10 to 14 and Comparative Examples 4 to 10)
Using the substrate obtained in the above flatness evaluation, the presence or absence of scratches on the copper surface was examined in the dark field using an optical microscope after the second polishing step of 4 minutes was completed under the following polishing conditions. I observed it. The evaluation criteria are as follows. The results are also shown in Table 2.
(polishing conditions)
- Polishing device: Manufactured by G&P TECHNOLOGY, model "POLI-400L"
・Polishing pad: “IC1000” manufactured by Nitta Haas
・Chemical mechanical polishing composition supply rate: 200 mL/min ・Surface plate rotation speed: 100 rpm
・Head rotation speed: 90rpm
・Pressing pressure of polishing head: 140hPa
(Evaluation criteria)
- If there were no scratches, the surface condition was judged to be good and was marked as "○".
- If there are scratches, it is judged that the surface condition is poor and is marked with an "x".
２．４．５．貯蔵安定性評価
上記のようにして各化学機械研磨用組成物を調製した後、常温・常圧で静置し、３０分間静置後の各組成物を目視にて観察することにより貯蔵安定性を評価した。評価基準は以下の通りである。その結果を表１及び表２に併せて示す。
（評価基準）
・３０分間静置後の組成物の状態が調製直後と比較して変化がない場合、「◎」と表記した。
・３０分間静置後の組成物に僅かに沈殿物が観察された場合、「○」と表記した。
2.4.5. Storage stability evaluation After each chemical mechanical polishing composition was prepared as described above, it was allowed to stand at room temperature and normal pressure, and the storage stability was determined by visually observing each composition after standing for 30 minutes. was evaluated. The evaluation criteria are as follows. The results are also shown in Tables 1 and 2.
(Evaluation criteria)
- If the state of the composition after standing for 30 minutes did not change compared to immediately after preparation, it was marked as "◎".
- If a slight precipitate was observed in the composition after standing for 30 minutes, it was marked as "○".
２．５．評価結果
各化学機械研磨用組成物の組成、物性、及び評価結果を下表１及び下表２に示す。
2.5. Evaluation Results The composition, physical properties, and evaluation results of each chemical mechanical polishing composition are shown in Tables 1 and 2 below.
下表１及び下表２において、各成分の数値は質量部を表す。また、表１及び表２における砥粒のうちアルミナ含有粒子の略称は、それぞれ以下の商品名を意味する。
＜アルミナ含有粒子＞
・ＡＡ－０４：アルミナ（住友化学株式会社製、商品名「ＡＡ－０４」）
・ＡＡ－０７：アルミナ（住友化学株式会社製、商品名「ＡＡ－０７」）
・ＡＡ－２：アルミナ（住友化学株式会社製、商品名「ＡＡ－２」）
・ＡＫＰ－２０：アルミナ（住友化学株式会社製、商品名「ＡＫＰ－２０」）
・ＡＫＰ－３０：アルミナ（住友化学株式会社製、商品名「ＡＫＰ－３０」）
・９２４５ ０．１５ＭＩＣ：アルミナ（ＳＡＩＮＴ－ＧＯＢＡＩＮ株式会社製、商品名「９２４５ ０．１５ＭＩＣ」）
In Table 1 and Table 2 below, the numerical value of each component represents parts by mass. Furthermore, among the abrasive grains in Tables 1 and 2, the abbreviations for alumina-containing particles mean the following trade names, respectively.
<Alumina-containing particles>
・AA-04: Alumina (manufactured by Sumitomo Chemical Co., Ltd., product name "AA-04")
・AA-07: Alumina (manufactured by Sumitomo Chemical Co., Ltd., product name "AA-07")
・AA-2: Alumina (manufactured by Sumitomo Chemical Co., Ltd., product name "AA-2")
・AKP-20: Alumina (manufactured by Sumitomo Chemical Co., Ltd., product name "AKP-20")
・AKP-30: Alumina (manufactured by Sumitomo Chemical Co., Ltd., product name "AKP-30")
・9245 0.15MIC: Alumina (manufactured by SAINT-GOBAIN Co., Ltd., product name "9245 0.15MIC")
実施例１～９の化学機械研磨用組成物を用いた場合は、樹脂膜を高研磨速度で研磨できると共に、樹脂膜及び銅を有する被研磨面の平坦性も良好であることが判明した。 It was found that when the chemical mechanical polishing compositions of Examples 1 to 9 were used, the resin film could be polished at a high polishing rate, and the flatness of the polished surface containing the resin film and copper was also good.
一方、比較例１～３の化学機械研磨用組成物を用いた場合は、アルミナ含有粒子の硬度
が樹脂膜を研磨するのに適していないため、樹脂膜に対する研磨速度が著しく低下した。また、樹脂膜に対する研磨速度が低すぎたため、平坦性評価を行うことができなかった。
On the other hand, when the chemical mechanical polishing compositions of Comparative Examples 1 to 3 were used, the hardness of the alumina-containing particles was not suitable for polishing the resin film, so the polishing rate for the resin film was significantly reduced. Furthermore, since the polishing rate for the resin film was too low, flatness evaluation could not be performed.
以上の結果から、本発明に係る化学機械研磨用組成物によれば、配線及び樹脂膜を有する回路基板を化学機械研磨する際に、樹脂膜に対する研磨速度が十分に高く、かつ、被研磨面を高平坦化できることが判明した。 From the above results, according to the chemical mechanical polishing composition of the present invention, when chemical mechanical polishing is applied to a circuit board having wiring and a resin film, the polishing rate for the resin film is sufficiently high, and the surface to be polished is It was found that it is possible to achieve a high level of flatness.
実施例１０～１４の化学機械研磨方法によれば、第１研磨工程において樹脂膜を高研磨速度で研磨できると共に、第２研磨工程において樹脂膜及び銅を有する被研磨面の平坦性も良好であり、銅面にスクラッチが発生していないことが確認された。 According to the chemical mechanical polishing methods of Examples 10 to 14, the resin film can be polished at a high polishing rate in the first polishing step, and the surface to be polished having the resin film and copper can have good flatness in the second polishing step. It was confirmed that there were no scratches on the copper surface.
一方、比較例４～６の化学機械研磨方法では、アルミナ含有粒子の硬度が樹脂膜を研磨
するのに適していないため、樹脂膜に対する研磨速度が著しく低下した。そのため、樹脂膜及び銅を有する被研磨面が表出せず、第２研磨工程を実施することができなかった。
On the other hand, in the chemical mechanical polishing methods of Comparative Examples 4 to 6, the hardness of the alumina-containing particles was not suitable for polishing the resin film, so the polishing rate for the resin film was significantly reduced. Therefore, the surface to be polished having the resin film and copper could not be exposed, making it impossible to perform the second polishing step.
また、比較例７～９の化学機械研磨方法では、第１研磨工程において、シリカ粒子を含有する化学機械研磨用組成物を使用したため、樹脂膜に対する研磨速度が著しく低下した。そのため、樹脂膜及び銅を有する被研磨面が表出せず、第２研磨工程を実施することができなかった。 Furthermore, in the chemical mechanical polishing methods of Comparative Examples 7 to 9, the polishing rate for the resin film was significantly reduced because a chemical mechanical polishing composition containing silica particles was used in the first polishing step. Therefore, the surface to be polished having the resin film and copper could not be exposed, making it impossible to perform the second polishing step.
比較例１０の化学機械研磨方法では、第１研磨工程において、シリカ粒子を含有する化学機械研磨用組成物を使用したため、樹脂膜に対する研磨速度が著しく低下した。その後、第２研磨工程において、アルミナ含有粒子（ＡＡ－０４）を含有する化学機械研磨用組成物を使用して研磨を試みたが、被研磨面の表面が荒れており、銅面にはスクラッチが認められた。 In the chemical mechanical polishing method of Comparative Example 10, since a chemical mechanical polishing composition containing silica particles was used in the first polishing step, the polishing rate for the resin film was significantly reduced. After that, in the second polishing step, polishing was attempted using a chemical mechanical polishing composition containing alumina-containing particles (AA-04), but the surface to be polished was rough and there were scratches on the copper surface. was recognized.
以上の結果から、本発明に係る化学機械研磨方法によれば、第１研磨工程において樹脂膜を高研磨速度で研磨できると共に、第２研磨工程において樹脂膜及び銅を有する被研磨面の平坦性も良好であり、銅面にスクラッチが発生せず、良好な回路基板を作成できることが判明した。 From the above results, according to the chemical mechanical polishing method according to the present invention, the resin film can be polished at a high polishing rate in the first polishing step, and the flatness of the surface to be polished including the resin film and copper can be improved in the second polishing step. It was also found that a good circuit board could be produced without scratches on the copper surface.
本発明は、上述した実施形態に限定されるものではなく、種々の変形が可能である。例えば、本発明は、実施形態で説明した構成と実質的に同一の構成（例えば、機能、方法および結果が同一の構成、あるいは目的および効果が同一の構成）を含む。また、本発明は、実施形態で説明した構成の本質的でない部分を置き換えた構成を含む。また、本発明は、実施形態で説明した構成と同一の作用効果を奏する構成または同一の目的を達成することができる構成を含む。また、本発明は、実施形態で説明した構成に公知技術を付加した構成を含む。 The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as those described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objectives and effects). Further, the present invention includes a configuration in which non-essential parts of the configuration described in the embodiments are replaced. Further, the present invention includes a configuration that has the same effects or a configuration that can achieve the same objective as the configuration described in the embodiment. Further, the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.
１…アルミナ含有粒子、１０…配線金属、１２…樹脂膜、４２…スラリー供給ノズル、４４…スラリー（化学機械研磨用組成物）、４６…研磨布、４８…ターンテーブル、５０…回路基板、５２…キャリアーヘッド、５４…水供給ノズル、５６…ドレッサー、１００…被処理体、２００…回路基板、３００…化学機械研磨装置 DESCRIPTION OF SYMBOLS 1... Alumina-containing particle, 10... Wiring metal, 12... Resin film, 42... Slurry supply nozzle, 44... Slurry (chemical mechanical polishing composition), 46... Polishing cloth, 48... Turntable, 50... Circuit board, 52 ...Carrier head, 54...Water supply nozzle, 56...Dresser, 100...Object to be processed, 200...Circuit board, 300...Chemical mechanical polishing device
Claims (7)
前記第１研磨工程後の被研磨面を、さらに（Ａ２）シリカ粒子を含有する第２化学機械研磨用組成物を使用して研磨する第２研磨工程と、
を含み、
前記（Ａ１）アルミナ含有粒子が、粉末Ｘ線回折パターンにおける回折強度が最大となるピーク部分の半値幅が０．３０°未満のものである、化学機械研磨方法。 (A1) a first polishing step of polishing a surface to be polished containing resin using a first chemical mechanical polishing composition containing alumina-containing particles;
A second polishing step of polishing the surface to be polished after the first polishing step using a second chemical mechanical polishing composition containing (A2) silica particles;
including;
A chemical mechanical polishing method, wherein the alumina-containing particles (A1) have a half-value width of less than 0.30° at a peak portion where the diffraction intensity is maximum in a powder X-ray diffraction pattern.
に記載の化学機械研磨方法。The chemical mechanical polishing method described in .
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| JP7370904B2 (en) | 2020-03-05 | 2023-10-30 | 株式会社トッパンインフォメディア | Method for polishing interlayer insulation material of semiconductor package substrate |
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| US8623766B2 (en) * | 2011-09-20 | 2014-01-07 | Cabot Microelectronics Corporation | Composition and method for polishing aluminum semiconductor substrates |
| US9752057B2 (en) * | 2014-02-05 | 2017-09-05 | Cabot Microelectronics Corporation | CMP method for suppression of titanium nitride and titanium/titanium nitride removal |
| JP6130316B2 (en) * | 2014-03-11 | 2017-05-17 | 信越化学工業株式会社 | Polishing composition, polishing method, and method for producing polishing composition |
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| JP2003512501A (en) | 1999-10-15 | 2003-04-02 | サンーゴバン セラミックス アンド プラスティクス，インコーポレイティド | Improved CMP product |
| JP2004022748A (en) | 2002-06-14 | 2004-01-22 | Seimi Chem Co Ltd | Method for polishing organic insulating film in semiconductor integrated circuit |
| US20050032465A1 (en) | 2003-08-08 | 2005-02-10 | Shigeo Fujii | Substrate for magnetic disk |
| JP2005063530A (en) | 2003-08-08 | 2005-03-10 | Kao Corp | Substrate for magnetic disk |
| JP2009163808A (en) | 2007-12-28 | 2009-07-23 | Kao Corp | Polishing liquid composition for hard disk substrate |
| JP2014229827A (en) | 2013-05-24 | 2014-12-08 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing and method for chemical mechanical polishing |
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| JP2022160391A (en) | 2022-10-19 |
| TW201939598A (en) | 2019-10-01 |
| JP2019157120A (en) | 2019-09-19 |
| TWI786275B (en) | 2022-12-11 |
| JP7183863B2 (en) | 2022-12-06 |
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